Ink jet liquid composition and ink jet recording method

ABSTRACT

An ink jet liquid composition contains an organic solvent, a polymerizable compound, a photopolymerization initiator, and a polyether-modified siloxane compound having a weight-average molecular weight of 3,000 or more, and the content of the organic solvent is 40% by mass or more and 90% by mass or less with respect to the total mass of the composition. In addition, an ink jet recording method using the ink jet liquid composition is provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of International Application No.PCT/JP2018/004069, filed Feb. 6, 2018, the disclosure of which isincorporated herein by reference in its entirety. Further, thisapplication claims priority from Japanese Patent Application No.2017-037215, filed Feb. 28, 2017, the disclosure of which isincorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present disclosure relates to an ink jet liquid composition and anink jet recording method.

2. Description of the Related Art

As an image recording method of forming an image on a recording mediumsuch as paper or plastic, based on an image data signal, there are anelectrophotographic method, a sublimation-type or fusion-type thermaltransfer method, a screen printing method, and an ink jet method.

In the ink jet method, a printing device is inexpensive, a plate is notrequired at the time of printing, and image formation is directlycarried out on a recording medium by jetting an ink composition only toa necessary image area. Thus, the ink composition can be used withexcellent efficiency, and the running cost becomes low particularly in acase of small lot production. Further, the ink jet method generateslittle noise and is excellent as an image recording method. Therefore,the ink jet method has been attracting attention in recent years.

In addition, as an ink jet ink, a solvent ink, an aqueous ink, anultraviolet curable-type ink, an ultraviolet curable-type solvent ink(solvent UV ink), and the like may be exemplified.

Conventional ink jet ink compositions include compounds described inJP2006-181801A, JP2016-020457A, JP2013-163740A, or JP2016-000819A.

SUMMARY OF THE INVENTION

An object of an embodiment of the present invention is to provide an inkjet liquid composition with which even in a case of forming a cured filmusing a base material having a concave-convex shape, the obtained curedfilm has excellent abrasion resistance and excellent chemicalresistance.

Another object of another embodiment of the present invention to providean ink jet recording method using the ink jet liquid composition.

Means for achieving the above objects includes the following aspects.

<1> An ink jet liquid composition comprising: an organic solvent; apolymerizable compound; a photopolymerization initiator; and apolyether-modified siloxane compound having a weight-average molecularweight of 3,000 or more, in which a content of the organic solvent is40% by mass or more and 90% by mass or less with respect to a total massof the composition.

<2> The ink jet liquid composition according to <1>, in which a contentof a siloxane structure of the polyether-modified siloxane compound is20% by mass or more with respect to a total mass of thepolyether-modified siloxane compound.

<3> The ink jet liquid composition according to <1> or <2>, in which thepolyether-modified siloxane compound has a weight-average molecularweight of 5,000 or more and 100,000 or less.

<4> The ink jet liquid composition according to any one of <1> to <3>,in which a content of the polyether-modified siloxane compound is 2% bymass or more and 15% by mass or less with respect to a total solidcontent of the composition.

<5> The ink jet liquid composition according to any one of <1> to <4>,in which a mass ratio of the polyether-modified siloxane compound andthe polymerizable compound is polyether-modified siloxanecompound:polymerizable compound=1:5 to 1:30.

<6> The ink jet liquid composition according to any one of <1> to <5>,in which the polymerizable compound includes a bifunctional urethaneacrylate oligomer.

<7> The ink jet liquid composition according to <6>, in which thebifunctional urethane acrylate oligomer has a weight-average molecularweight of 3,000 or more and 20,000 or less.

<8> The ink jet liquid composition according to any one of <1> to <7>,in which a colorant is not contained.

<9> The ink jet liquid composition according to any one of <1> to <8>that is an ink jet liquid composition to be applied to a base materialhaving a concave-convex shape in at least a part of a surface.

<10> An ink jet recording method comprising: a step of applying the inkjet liquid composition according to any one of <1> to <9> to a basematerial by an ink jet recording head.

<11> The ink jet recording method according to <10>, in which the basematerial is a base material having a concave-convex shape in at least apart of a surface.

<12> An ink jet recording method comprising: a step of preparing a basematerial having a decorative layer formed thereon; a step of applyingthe ink jet liquid composition according to <8> to the decorative layerby an ink jet recording head; a step of drying the ink jet liquidcomposition on the decorative layer by applying heat; and a step ofcuring the ink jet liquid composition by irradiating the ink jet liquidcomposition with an ultraviolet ray, in which the base material havingthe decorative layer formed thereon has a concave-convex shape in atleast a part of a surface.

According to an embodiment of the present invention, it is possible toprovide an ink jet liquid composition with which even in a case offorming a cured film using a base material having a concave-convexshape, the obtained cured film has excellent abrasion resistance andexcellent chemical resistance.

According to another embodiment of the present invention, it is possibleto provide an ink jet recording method using the ink jet liquidcomposition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the present disclosure will be described in detail.

In present specification, “xx to yy” refers to a numerical value rangethat includes xx and yy.

In present specification, the term “(meta)acrylic” is a term used as aconcept encompassing both acrylic and methacrylic, and the term“(meth)acryloyl” is a term used as a concept encompassing both acryloyland methacryloyl.

A hydrocarbon group such as an alkyl group, an aryl group, an alkylenegroup or an arylene group in the present disclosure may have a branch ora ring structure unless otherwise specified.

In addition, in the present disclosure, “% by mass” and “% by weight”are the same and “parts by mass” and “parts by weight” are the same.

In addition, the term “step” in the present specification means not onlyan independent step but also a step in which an expected object in thestep is attained even in a case where the step cannot be clearlydistinguished from other steps. In addition, in the present disclosure,a combination of two or more preferable embodiments is a more preferableembodiment.

Further, the weight-average molecular weight (Mw) in the presentdisclosure is a molecular weight detected by using a gel permeationchromatography (GPC) analyzer using columns of TSKgel GMHxL, TSKgelG4000HxL, and TSKgel G2000HxL (all trade name, manufactured by TosohCorporation), tetrahydrofuran (THF) as a solvent, and a differentialrefractometer and shown in terms of polystyrene as a standard substance,unless otherwise specified.

Hereinafter, the present disclosure will be described in detail.

(Ink Jet Liquid Composition)

An ink jet liquid composition according to an embodiment of the presentdisclosure (hereinafter, also simply referred to as a “liquidcomposition”) contains an organic solvent, a polymerizable compound, aphotopolymerization initiator, and a polyether-modified siloxanecompound having a weight-average molecular weight of 3,000 or more, anda content of the organic solvent is 40% by mass or more and 90% by massor less with respect to the total mass of the composition.

As a result of detailed examinations conducted by the present inventors,it has been found that by adopting an ink jet liquid composition havingthe above composition, even in a case where a cured film is formed usinga base material having a concave-convex shape, the obtained cured filmhas excellent abrasion resistance and excellent chemical resistance.

Although the detailed mechanism is unknown, it is assumed that bysetting the content of the organic solvent to 40% by mass or more and90% by mass or less with respect to the total mass of the liquidcomposition, a dried film with a thin film thickness in which componentsother than the organic solvent are uniformly applied is easily formedand cured to obtain a tough cured film so that the obtained cured filmhas excellent abrasion resistance and excellent chemical resistance.

In addition, by containing the polyether-modified siloxane compoundhaving a weight-average molecular weight of 3,000 or more, the viscosityincrease in the composition at the time of drying is fast, even in acase where a base material having a concave-convex shape is used,followability to the concave-convex shape is excellent, a compositionreservoir is prevented from being formed in the concave portion, and acured film is prevented from not being formed or a thin portion isprevented from being formed in the convex portion, and further, a toughcured film is obtained. Thus, it is assumed that the obtained cured filmhas excellent abrasion resistance and excellent chemical resistance.

Hereinafter, the present disclosure will be described in detail.

The ink jet liquid composition according to the embodiment of thepresent disclosure can be suitably used as an ink jet liquid compositionto be applied to a base material having a concave-convex shape in atleast a part of the surface such as leather and can be more suitablyused as an ink jet liquid composition to be applied to leather.

Regarding the term “to be applied to the base material”, the liquidcomposition may be directly applied to the base material or after alayer such as a decorative layer is provided to the base material, theliquid composition may be applied to the layer.

The leather is not particularly limited, and examples thereof includenatural leather, synthetic leather, and artificial leather. In addition,the above-mentioned leather may be one subjected to treatment such astanning.

It is needless to say that the ink jet liquid composition according tothe embodiment of the present disclosure may be applied to a basematerial having a concave-convex shape in at least a part of the surfaceand a normal smooth base material.

The term “concave-convex shape” of the surface of the base material orthe surface of the base material on which a decorative layer, which willbe described later, is formed thereon in the present disclosure is aportion satisfying Expression R.

L2≥1.05×L1  Expression R

For L1 and L2, the following lengths are measured on the base materialby a confocal laser microscope.

L1: a projection length between a point A on the surface of the basematerial where the cross-sectional shape is analyzed by a confocal lasermicroscope and a point B on the same base material surface as the pointA (projection distance between point A and point B)

L2: a length from the point A calculated from the cross-sectional shapemeasured by a confocal laser microscope to the point B along theconcave-convex shape on the base material surface (length ofcross-sectional curve between point A and point B)

In a normal smooth base material, the value of L2 is less than 1.05times the value of L1.

As the confocal laser microscope, a shape analysis laser microscope(VK-X 250/260) manufactured by Keyence Corporation may be suitably used.

In addition, from the viewpoint of further exerting the effects of theliquid composition according to the embodiment of the presentdisclosure, the base material used in the present disclosure ispreferably a base material having a portion satisfying Expression R-1 inat least a part of the surface, more preferably a base material having aportion satisfying Expression R-2 in at least a part of the surface, andeven more preferably a base material having a portion satisfyingExpression R-3 in at least a part of the surface.

L2≥1.10×L1  Expression R-1

5×L1≥L2≥1.10×L1  Expression R-2

3×L1≥L2≥1.20×L1  Expression R-3

The base material used in the present disclosure is preferably a basematerial having a concave-convex shape in an area of 50% by area or moreof the surface on at least one surface, and more preferably a basematerial having a concave-convex shape in an area of 70% by area or moreof the surface on at least one surface.

The liquid composition according to the embodiment of the presentdisclosure is an ink composition that is curable by active radiation.The term “active radiation” refers to a radiation capable of impartingenergy to generate an initiating species in the liquid composition bythe irradiation and includes an α-ray, a γ-ray, an X-ray, an ultravioletray, a visible ray, an electron beam and the like. Among these, from theviewpoint of curing sensitivity and easy availability of the apparatus,an ultraviolet ray, and an electron beam are preferable and anultraviolet ray is more preferable.

The liquid composition according to the embodiment of the presentdisclosure preferably contains as little water as possible and even in acase where the liquid composition contains water, the water content ispreferably 5% by mass or less, more preferably 1% by mass or less, andeven more preferably 0.5% by mass or less with respect to the total massof the liquid composition.

In addition, the liquid composition according to the embodiment of thepresent disclosure can be used for various applications such as an inkcomposition, a resist, an image recording layer of a planographicprinting plate precursor, a coating agent, a paint, an adhesive, apressure sensitive adhesive, a coating composition, a functional film, afilm, an optical material, a printing plate material, a semiconductormaterial, a recording material, a paper additive, a medical material, aplastic, a functional gel, and a cosmetic material. Among these, theliquid composition can be suitably used for a coating composition or anink composition and more suitably used for a coating composition.

Further, the liquid composition can be more suitably used for a coatingcomposition for protecting the decorative layer on the base material,and particularly suitably used for a coating composition for protectinga decorative layer on leather.

Hereinafter, each component used in the liquid composition according tothe embodiment of the present disclosure will be described in detail.

<Organic Solvent>

The ink jet liquid composition according to the embodiment of thepresent disclosure contains an organic solvent, and the content of theorganic solvent is 40% by mass or more and 90% by mass or less withrespect to the total mass of the liquid composition.

As the organic solvent, known solvents used for solvent inks and activeradiation curable solvent inks can be used, and examples thereof includeorganic solvents described in New Edition Solvent Pocketbook (TheSociety of Synthetic Organic Chemistry, Japan, 1994).

In addition, the organic solvent is preferably an organic solvent havinga boiling point of 150° C. or higher and 250° C. or lower and morepreferably an organic solvent having a boiling point of 150° C. orhigher and 200° C. or lower from the viewpoint of ink jet jettability,and the abrasion resistance and chemical resistance of the obtainedcured film.

The organic solvents that can be used in the present disclosure may beused singly or in combination of two or more thereof.

Examples of the organic solvent include (poly)alkylene glycol monoalkylethers such as diethylene glycol monoethyl ether, triethylene glycolmonomethyl ether, dipropylene glycol monomethyl ether, and tripropyleneglycol monomethyl ether, (poly)alkylene glycol dialkyl ethers such asethylene glycol dibutyl ether, diethylene glycol dimethyl ether,diethylene glycol diethyl ether, dipropylene glycol diethyl ether, andtetraethylene glycol dimethyl ether, (poly)alkylene glycol acetates suchas diethylene glycol acetate, (poly)alkylene glycol diacetates such asethylene glycol diacetate and propylene glycol diacetate, (poly)alkyleneglycol monoalkyl ether acetates such as ethylene glycol monobutyl etheracetate and propylene glycol monomethyl ether acetate, ketones such asmethyl ethyl ketone and cyclohexanone, lactones such as γ-butyrolactone,esters such as ethyl acetate, propyl acetate, butyl acetate,3-methoxybutyl acetate, methyl propionate, and ethyl propionate, cyclicethers such as tetrahydrofuran and dioxane, and amides such asdimethylformamide and dimethylacetamide.

In addition, as the (poly)alkylene glycol is preferably at least onecompound selected from the group consisting of (poly)ethylene glycol and(poly)propylene glycol.

Among these, from the viewpoint of ink jet jettability, and the chemicalresistance of the obtained cured film, it is preferable to use at leastone organic solvent selected from the group consisting of alkyleneglycol monoalkyl ether acetates, alkylene glycol monoalkyl ethers,alkylene glycol dialkyl ethers, alkylene glycol acetates, polyalkyleneglycol monoalkyl ether acetates, polyalkylene glycol monoalkyl ethers,polyalkylene glycol dialkyl ethers, polyalkylene glycol acetates,ketones, lactones, and esters, it is more preferable to use at least oneorganic solvent selected from the group consisting of alkylene glycolmonoalkyl ether acetates, alkylene glycol dialkyl ethers, polyalkyleneglycol monoalkyl ether acetates, polyalkylene glycol dialkyl ethers,ketones, lactones, and esters, it is even more preferable to use esters,and it is particularly preferable to use 3-methoxybutyl acetate.

The content of the organic solvent in the ink jet liquid compositionaccording to the embodiment of the present disclosure is 40% by mass ormore and 90% by mass or less with respect to the total mass of theliquid composition, and is preferably 50% by mass or more and 88% bymass or less, more preferably 65% by mass or more and 86% by mass orless, and particularly preferably 75% by mass or more and 84% by mass orless from the viewpoint of ink jet jettability and the abrasionresistance, bendability, and chemical resistance of the obtained curedfilm.

<Polyether-Modified Siloxane Compound Having Weight-Average MolecularWeight of 3,000 or More>

The ink jet liquid composition according to the embodiment of thepresent disclosure contains a polyether-modified siloxane compoundhaving a weight-average molecular weight of 3,000 or more.

The polyether-modified siloxane compound in the present disclosure isnot particularly limited as long as the polyether-modified siloxanecompound is a compound having a polyether structure and a siloxanestructure. However, from the viewpoint of ink jet jettability, and theabrasion resistance, chemical resistance, and adhesiveness of theobtained cured film, the content of a siloxane structure of apolyether-modified siloxane compound is preferably 15% by mass or more,more preferably 20% by mass or more, even more preferably 20% by mass ormore and 90% by mass or less, and particularly preferably 20% by mass ormore and 50% by mass or less with respect to the total mass of thepolyether-modified siloxane compound.

In the present disclosure, the content of the siloxane structure of thepolyether-modified siloxane compound can be quantitatively determined byvarious nuclear magnetic resonance (NMR) analysis and MALDI-MS analysis(mass spectrometry using matrix-assisted laser desorption ionization).

The siloxane structure may be a —(SiR^(S1)R^(S2))_(n)— structure (R^(S1)and R^(S2) each independently represent a hydrogen atom, a hydroxygroup, an alkoxy group, an alkyl group or an aryl group, and nrepresents an integer of 1 or more), and is preferably at least onestructure selected from the group consisting of a polydialkylsiloxanestructure and a polyalkylaryl siloxane structure, more preferably apolydialkylsiloxane structure, and particularly preferably apolydimethylsiloxane structure.

As the polyether structure, a polyalkyleneoxy structure is preferablyexemplified, and at least one structure selected from the groupconsisting of a polyethyleneoxy structure and a polypropyleneoxystructure is more preferably exemplified.

The weight-average molecular weight of the polyether-modified siloxanecompound used in the ink jet liquid composition according to the presentdisclosure is 3,000 or more, from the viewpoint of ink jet jettability,and the bendability and adhesiveness of the obtained cured film, ispreferably 5,000 or more, more preferably 5,000 or more and 100,000 orless, even more preferably 8,000 or more and 50,000 or less, andparticularly preferably 10,000 or more and 20,000 or less.

As the polyether-modified siloxane compound having a weight-averagemolecular weight of 3,000 or more, a commercially available product maybe used. Examples of commercially available products include KP109,KP368, KP306, KP341, KF-96H-10,000 CS, KF-96H-30,000 CS, andKF-96H-100,000 CS (all manufactured by Shin-Etsu Chemical Co., Ltd.),and BYK-UV3500 (manufactured by BYK Chemie GmbH).

These polyether-modified siloxane compounds may be used singly or incombination of two or more thereof.

The content of the polyether-modified siloxane compound in the ink jetliquid composition according to the present disclosure is preferably 1%by mass or more and 20% by mass or less, more preferably 2% by mass ormore and 15% by mass or less, and particularly preferably 2.5% by massor more and 10% by mass or less with respect to the total solid contentof the composition from the viewpoint of ink jet jettability, and theabrasion resistance, chemical resistance, and adhesiveness of theobtained cured film. The “solid content” in the composition represents acomponent excluding volatile components such as an organic solvent.

In addition, in the ink jet liquid composition according to the presentdisclosure, the mass ratio of the polyether-modified siloxane compoundand the polymerizable compound is preferably polyether-modified siloxanecompound:polymerizable compound=1:3 to 1:50 and more preferably 1:5 to1:30 from the viewpoint of ink jet jettability, and the abrasionresistance, chemical resistance, and adhesiveness of the obtained curedfilm.

Further, in the ink jet liquid composition according to the presentdisclosure, the mass ratio of the polyether-modified siloxane compoundand a vinyl chloride-vinyl acetate copolymer described later ispreferably polyether-modified siloxane compound:vinyl chloride-vinylacetate copolymer=10:1 to 1:1, more preferably 5:1 to 1:1, and even morepreferably 5:1 to 2:1 from the viewpoint of the abrasion resistance,chemical resistance, and adhesiveness of the obtained cured film.

<Polymerizable Compound>

The ink jet liquid composition according to the present disclosureincludes a polymerizable compound.

The polymerizable compound is not particularly limited as long as thecompound is a compound that causes a polymerization reaction uponapplication of any energy to be cured, and any kind of monomer, oligomeror polymer can be used. In particular, various known polymerizablemonomers known as radical polymerizable monomers, which cause apolymerization reaction by initiating species generated from apolymerization initiator added as requested, are preferable.

In addition, the polymerizable compound is preferably an ethylenicallyunsaturated compound.

Further, the polymerizable compound in the present disclosure is acompound other than the polyether-modified siloxane compound having aweight-average molecular weight of 3,000 or more, and is preferably acompound which does not have both a polyether structure and a siloxanestructure.

The polymerizable compound can be used as a mixture of one or more forthe purpose of adjusting the reaction rate, the physical properties ofthe cured film, the physical properties of the composition, and thelike. In addition, the polymerizable compound may be a monofunctionalcompound or a polyfunctional compound. In a case where the ratio of themonofunctional polymerizable compound is large, the cured product easilybecomes flexible, and in a case where the ratio of the polyfunctionalpolymerizable compound is large, the curability easily becomesexcellent. Accordingly, the ratio between the monofunctionalpolymerizable compound and the polyfunctional polymerizable compound isarbitrarily determined according to the application.

The polymerizable compound used in the present disclosure preferablycontains a urethane (meth)acrylate oligomer from the viewpoints of theabrasion resistance, bendability, and chemical resistance of theobtained cured film.

The urethane (meth)acrylate oligomer in the present disclosure may be acompound having one or more urethane bonds and having a (meth)acryloxygroup.

It is preferable that the ink jet liquid composition according to theembodiment of the present disclosure includes a bifunctional urethane(meth)acrylate oligomer from the viewpoint of the abrasion resistance,bendability, and chemical resistance of the obtained cured film, and itis more preferable that the weight-average molecular weight of thebifunctional urethane (meth)acrylate oligomer is 3,000 or more and20,000 or less from the viewpoint of the abrasion resistance,bendability, and chemical resistance of the obtained cured film.

Also, in the present disclosure, the oligomer has a weight-averagemolecular weight of 500 or more and 20,000 or less, and the polymer hasa weight-average molecular weight of more than 20,000.

As the bifunctional urethane (meth)acrylate oligomer, a commerciallyavailable product may be used.

Examples of the commercially available product include CN9001(manufactured by Sartomer Company Inc.), and SHIKO UV-3200B, SHIKOUV-3300B, SHIKO UV-3310B, and SHIKO UV-6630B (all manufactured by TheNippon Synthetic Chemical Industry Co., Ltd.).

In addition, the polymerizable compound used in the present disclosurepreferably includes a trifunctional or higher functional urethane(meth)acrylate oligomer and more preferably includes a bifunctionalurethane (meth)acrylate oligomer and a trifunctional or higher urethane(meth)acrylate oligomer from the viewpoint of the abrasion resistance,bendability, and chemical resistance of the obtained cured film.

The functional number of the trifunctional or higher urethane(meth)acrylate oligomer is preferably 3 or more and 12 or less, and morepreferably 3 or more and 6 or less from the viewpoint of the abrasionresistance, bendability, and chemical resistance of the obtained curedfilm.

In a case where as the polymerizable compound, a bifunctional urethane(meth)acrylate oligomer and a trifunctional or higher urethane(meth)acrylate oligomer are used in combination, the content ratio (massratio) of the bifunctional urethane (meth)acrylate oligomer and thetrifunctional or higher urethane (meth)acrylate oligomer in the ink jetliquid composition according to the embodiment of the present disclosureis preferably bifunctional urethane (meth)acrylateoligomer:trifunctional or higher urethane (meth)acrylate oligomer=3:1 to1:2, more preferably 2:1 to 1:1.5, and even more preferably 1.5:1 to1:1.5 from the viewpoint of the abrasion resistance, bendability, andchemical resistance of the obtained cured film.

As the trifunctional or higher urethane (meth)acrylate oligomer, acommercially available product may be used.

Examples of commercially available products include SHIKO UV-7600B andSHIKO UV-7550B (all manufactured by Nippon Synthetic Chemical IndustryCo., Ltd.).

The weight-average molecular weight (Mw) of the urethane (meth)acrylateoligomer is preferably 500 or more and 20,000 or less, more preferably1,000 or more and 10,000 or less, and even more preferably 1,200 or moreand 6,000 or less from the viewpoint of the abrasion resistance,bendability, and chemical resistance of the obtained cured film.

The content of the urethane (meth)acrylate oligomer in the ink jetliquid composition according to the embodiment of the present disclosureis preferably 1% by mass or more and 50% by mass or less, morepreferably 3% by mass or more and 30% by mass or less, and particularlypreferably 5% by mass or more and 20% by mass or less with respect tothe total mass of the composition from the viewpoint of the abrasionresistance, bendability, and chemical resistance of the obtained curedfilm.

In addition, the content of the bifunctional urethane (meth)acrylateoligomer in the ink jet liquid composition according to the embodimentof the present disclosure is preferably 0.5% by mass or more and 50% bymass or less, more preferably 1% by mass or more and 20% by mass orless, and particularly preferably 2% by mass or more and 10% by mass orless with respect to the total mass of the composition from theviewpoint of the abrasion resistance, bendability, and chemicalresistance of the obtained cured film.

In addition, the content of the trifunctional or higher urethane(meth)acrylate oligomer in the ink jet liquid composition according tothe embodiment of the present disclosure is preferably 0.5% by mass ormore and 20% by mass or less, more preferably 1% by mass or more and 15%by mass or less, and particularly preferably 2% by mass or more and 10%by mass or less with respect to the total mass of the composition fromthe viewpoint of the abrasion resistance, bendability, and chemicalresistance of the obtained cured film.

In addition, examples of the polymerizable compound include(meth)acrylate compounds, (meth)acrylamide compounds, and aromatic vinylcompounds.

Examples of (meth)acrylate compounds used as the polymerizable compoundinclude monofunctional (meth)acrylate compounds, bifunctional(meth)acrylate compounds, trifunctional (meth)acrylate compounds,tetrafunctional (meth)acrylate compounds, pentafunctional (meth)acrylatecompounds, and hexafunctional (meth)acrylate compounds.

Examples of the monofunctional (meth)acrylate compounds include hexyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, tert-octyl (meth)acrylate,isoamyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate,stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl(meth)acrylate, 4-n-butylcyclohexyl (meth)acrylate, bornyl(meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate,2-ethylhexyldiglycol (meth)acrylate, butoxyethyl (meth)acrylate,2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl(meth)acrylate, benzyl (meth)acrylate, butoxymethyl (meth)acrylate,3-methoxybutyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate,2-(2-butoxyethoxy)ethyl (meth)acrylate, 2,2,2-tetrafluoroethyl(meth)acrylate, 1H,1H,2H,2H-perfluorodecyl (meth)acrylate, 4-butylphenyl(meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl(meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl(meth)acrylate, phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate,glycidyloxybutyl (meth)acrylate, glycidyloxyethyl (meth)acrylate,glycidyloxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate,2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate,2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate.

4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate,dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate,dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate,trimethoxysilylpropyl (meth)acrylate, trimethylsilylpropyl(meth)acrylate, polyethylene oxide monomethyl ether (meth)acrylate,oligoethylene oxide monomethyl ether (meth)acrylate, polyethylene oxide(meth)acrylate, oligoethylene oxide (meth)acrylate, oligoethylene oxidemonoalkyl ether (meth)acrylate, polyethylene oxide monoalkyl ether(meth)acrylate, dipropylene glycol (meth)acrylate, polypropylene oxidemonoalkyl ether (meth)acrylate, oligopropylene oxide monoalkyl ether(meth)acrylate, 2-methacryloyloxyethylsuccinic acid,2-methacryloyloxyhexahydrophthalic acid,2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethyleneglycol (meth)acrylate, trifluoroethyl (meth)acrylate,perfluorooctylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, ethylene oxide (EO)-modified phenol (meth)acrylate,EO-modified cresol (meth)acrylate, EO-modified nonyl phenol(meth)acrylate, propylene oxide (PO)-modified nonyl phenol(meth)acrylate, EO-modified 2-ethylhexyl (meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyl oxy ethyl (meth)acrylate, andicyclopentanyl (meth)acrylate, (3-ethyl-3-oxetanyl methyl)(meth)acrylate, and phenoxyethylene glycol (meth)acrylate.

Examples of bifunctional (meth)acrylate compounds include 1,6-hexanedioldi(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycoldi(meth)acrylate, 2,4-dimethyl-1,5-pentanediol di(meth)acrylate,3-methyl-1,5-pentanediol di(meth)acrylate, butylethylpropanedioldi(meth)acrylate, ethoxylated cyclohexane methanol di(meth)acrylate,polyethylene glycol di(meth)acrylate, oligoethylene glycoldi(meth)acrylate, ethylene glycol di(meth)acrylate,2-ethyl-2-butyl-butanediol di(meth)acrylate, hydroxypivalic acidneopentyl glycol di(meth)acrylate, EO-modified bisphenol Adi(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, polypropyleneglycol di(meth)acrylate, oligopropylene glycol di(meth)acrylate,1,4-butanediol di(meth)acrylate, 2-ethyl-2-butylpropanedioldi(meth)acrylate, 1,9-nonane di(meth)acrylate, propoxylated ethoxylatedbisphenol A di(meth)acrylate, tricyclodecane di(meth)acrylate,dipropylene glycol di(meth)acrylate, tripropylene glycoldi(meth)acrylate, and PO-modified neopentyl glycol di(meth)acrylate.

Examples of trifunctional (meth)acrylate compounds includetrimethylolpropane tri(meth)acrylate, trimethylolethanetri(meth)acrylate, trimethylolpropane alkylene oxide-modifiedtri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritoltri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxypropyl)ether,isocyanuric acid alkylene oxide-modified tri(meth)acrylate, propionicacid dipentaerythritol tri(meth)acrylate, tri((meth)acryloyloxyethyl)isocyanurate, hydroxypival aldehyde-modified dimethylolpropanetri(meth)acrylate, sorbitol tri(meth)acrylate, propoxylatedtrimethylolpropane tri(meth)acrylate, and ethoxylated glycerintriacrylate.

Examples of tetrafunctional (meth)acrylate compounds includepentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate,ditrimethylolpropane tetra(meth)acrylate, propionic aciddipentaerythritol tetra(meth)acrylate, and ethoxylated pentaerythritoltetra(meth)acrylate.

Examples of pentafunctional (meth)acrylate compounds include sorbitolpenta(meth)acrylate and dipentaerythritol penta(meth)acrylate.

Examples of hexafunctional (meth)acrylate compounds includedipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate,phosphazene alkylene oxide-modified hexa(meth)acrylate, andε-caprolactone-modified dipentaerythritol hexa(meth)acrylate.

Examples of (meth)acrylamide compounds used as the radical polymerizablecompound include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl (meth)acrylamide, N-n-butyl (meth)acrylamide,N-t-butyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl (meth)acrylamide, and (meth)acryloylmorpholine.

Examples of aromatic vinyls used as the radical polymerizable compoundinclude styrene, dimethyl styrene, trimethyl styrene, isopropyl styrene,chloromethyl styrene, methoxy styrene, acetoxy styrene, chlorostyrene,dichlorostyrene, bromostyrene, methyl ester vinylbenzoate, 3-methylstyrene, 4-methyl styrene, 3-ethyl styrene, 4-ethyl styrene, 3-propylstyrene, 4-propyl styrene, 3-butyl styrene, 4-butyl styrene, 3-hexylstyrene, 4-hexyl styrene, 3-octyl styrene, 4-octyl styrene,3-(2-ethylhexyl) styrene, 4-(2-ethylhexyl) styrene, allyl styrene,isopropenyl styrene, butenyl styrene, octenyl styrene,4-t-butoxycarbonyl styrene, and 4-t-butoxy styrene.

Further, examples of the radical polymerizable compound in the presentdisclosure include vinyl ester compounds (such as vinyl acetate, vinylpropionate, and vinyl versate), allyl ester compounds (such as allylacetate), halogen-containing monomers (such as vinylidene chloride, andvinyl chloride), vinyl ethers (such as methyl vinyl ether, butyl vinylether, hexyl vinyl ether, methoxy vinyl ether, 2-ethyl hexyl vinylether, methoxyethyl vinyl ether, cyclohexyl vinyl ether, chloroethylvinyl ether, and triethyleneglycol divinyl ether), vinyl cyanides (suchas (meth)acrylonitrile), and olefin compounds (such as ethylene, andpropylene), and N-vinyl lactam compounds (such as N-vinylcaprolactam).

More specifically, commercially available products or radicallypolymerizable or crosslinking monomers, oligomers, and polymers that areindustrially known, such as those described in “Crosslinking AgentHandbook” edited by Shinzo Yamashita (1981, Taiseisha Ltd.); “UV⋅EBCuring Handbook (raw material edition)” edited by Kiyoshi Kato (1985,Koubunshi Kankoukai); “Application and Market of UV⋅EB CuringTechnique”, p. 79, edited by RadTech Japan (1989, CMC Publishing Co.,Ltd.); “Polyester Resin Handbook” edited by Eiichiro Takiyama (1988, TheNikkan Kogyo Shimbun, Ltd.) and the like can be used.

These polymerizable compounds may be used singly or in combination oftwo or more thereof.

The content of the polymerizable compound in the ink jet liquidcomposition according to the embodiment of the present disclosure isalso related to the application, but is preferably 10% by mass to 95% bymass and more preferably 20% by mass to 90% by mass with respect to thetotal solid content of the composition from the viewpoint of curability.

From the viewpoint of the abrasion resistance, bendability, and chemicalresistance of the obtained cured film, the content of polymerizablecompounds other than the urethane (meth)acrylate oligomer in the ink jetliquid composition according to the embodiment of the present disclosureis preferably 50% by mass or less, more preferably 20% by mass or less,and even more preferably 5% by mass or less with respect to the totalsolid content of the composition and other polymerizable compounds areparticularly preferably not included in the composition.

<Photopolymerization Initiator>

The ink jet liquid composition according to the embodiment of thepresent disclosure contains a photopolymerization initiator.

As the photopolymerization initiator that can be used in the presentdisclosure, a photoradical polymerization initiator is preferably usedfrom the viewpoint of excellent curability and fixing property.

The photopolymerization initiator in the present disclosure is acompound that causes a chemical change through the action of light orinteraction with the electron excited state of a sensitizer to generatea polymerization initiating species, and among these compounds, from theviewpoint of initiating polymerization by simple means of exposure, aphotopolymerization initiator is preferable.

The photopolymerization initiator can be selected fromphotopolymerization initiators sensitive to active radiation to beemitted such as an ultraviolet ray in a range of 400 nm to 200 nm, a farultraviolet ray, a g-ray, an h-ray, an i-ray, a KrF excimer laser beam,an ArF excimer laser beam, an electron beam, an X-ray, a molecular beamor an ion beam.

Preferable examples of the photopolymerization initiator includes (a)aromatic ketones, (b) aromatic onium salts, (c) organic peroxides, (d)hexaarylbiimidazole compounds, (e) ketoxime ester compounds, (f) boratecompounds, (g) azinium compounds, (h) metallocene compounds, (i) activeester compounds, and (j) carbon-halogen bond-containing compounds.

As the photoradical polymerization initiator, from the viewpoint ofcurability, aromatic ketones are preferable.

In addition, as the photoradical polymerization initiator, anacylphosphine oxide compound is preferable.

As the acylphosphine oxide compound, a monoacylphosphine oxide compound,a bisacylphosphine oxide compound, and the like can be used, and as themonoacylphosphine oxide compound, a known monoacylphosphine oxidecompound can be used. Examples thereof include monoacylphosphine oxidecompounds described in JP1985-008047B (JP-S60-008047B) andJP1988-040799B (JP-S63-040799B). Specific examples thereof includemethyl isobutyrylmethylphosphinate, methyl isobutyrylphenylphosphinate,methyl pivaloylphenylphosphinate, methyl2-ethylhexanoylphenylphosphinate, isopropyl pivaloylphenylphosphinate,methyl p-toluylphenylphosphinate, methyl o-toluylphenylphosphinate,methyl 2,4-dimethylbenzoylphenylphosphinate, isopropylp-t-butylbenzoylphenylphosphinate, methyl acryloylphenylphosphinate,isobutyryldiphenylphosphine oxide, 2-ethylhexanoyldiphenylphosphineoxide, o-toluyldiphenylphosphine oxide,p-t-butylbenzoyldiphenylphosphine oxide,3-pyridylcarbonyldiphenylphosphine oxide, acryloyldiphenylphosphineoxide, benzoyldiphenylphosphine oxide, vinyl pivaloylphenylphosphinate,adipoylbisdiphenylphosphine oxide, pivaloyldiphenylphosphine oxide,p-toluyldiphenylphosphine oxide, 4-(t-butyl)benzoyldiphenylphosphineoxide, 2-methylbenzoyldiphenylphosphine oxide,2-methyl-2-ethylhexanoyldiphenylphosphine oxide,1-methylcyclohexanoyldiphenylphosphine oxide, methylpivaloylphenylphosphinate, and isopropyl pivaloylphenylphosphinate.

As the bisacylphosphine oxide compound, a known bisacylphosphine oxidecompound may be used. Examples thereof include bisacylphosphine oxidecompounds described in JP1991-101686A (JP-H03-101686A), JP1993-345790A(JP-H05-345790A), and JP1994-298818A (JP-H06-298818A). Specific examplesthereof include bis(2,6-dichlorobenzoyl)phenylphosphine oxide,bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide,bis(2,6-dichlorobenzoyl)-4-ethoxyphenylphosphine oxide,bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide,bis(2,6-dichlorobenzoyl)-2-naphthylphosphine oxide,bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide,bis(2,6-dichlorobenzoyl)-4-chlorophenylphosphine oxide,bis(2,6-dichlorobenzoyl)-2,4-dimethoxyphenylphosphine oxide,bis(2,6-dichlorobenzoyl)decylphosphine oxide,bis(2,6-dichlorobenzoyl)-4-octylphenylphosphine oxide,bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide,bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide,bis(2,6-dichloro-3,4,5-trimethoxybenzoyl)-2,5-dimethylphenylphosphineoxide, bis(2,6-dichloro-3,4,5-trimethoxybenzoyl)-4-ethoxyphenylphosphineoxide, bis(2-methyl-1-naphthoyl)-2,5-dimethylphenylphosphine oxide,bis(2-methyl-1-naphthoyl)-4-ethoxyphenylphosphine oxide,bis(2-methyl-1-naphthoyl)-2-naphthylphosphine oxide,bis(2-methyl-1-naphthoyl)-4-propylphenylphosphine oxide,bis(2-methyl-1-naphthoyl)-2,5-dimethylphenylphosphine oxide,bis(2-methoxy-1-naphthoyl)-4-ethoxyphenylphosphine oxide,bis(2-chloro-1-naphthoyl)-2,5-dimethylphenylphosphine oxide, andbis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide.

Among them, as the acylphosphine oxide compound in the presentdisclosure, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE819: manufactured by BASF SE),bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide,2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TPO: manufacturedby BASF SE, LUCIRIN TPO: manufactured by BASF SE),1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one(IRGACURE 2959: manufactured by BASF SE), and the like are preferable.

The photopolymerization initiator may be used singly or in combinationof two or more thereof. In addition, as long as the effects of theliquid composition according to the embodiment of the present disclosureare not impaired, a known sensitizer for the purpose of improvingsensitivity can be used in combination.

The ink jet liquid composition according to the embodiment of thepresent disclosure may contain, as the photopolymerization initiator, acompound that functions as a sensitizer (hereinafter also simplyreferred to as a “sensitizer”) in order to absorb a specific actinic rayto promote decomposition of the photopolymerization initiator.

Examples of the sensitizer include polynuclear aromatic compounds (suchas pyrene, perylene, triphenylene, and 2-ethyl-9,10-dimethoxyanthracene), xanthenes (such as fluorescein, eosin, erythrosine,rhodamine B, and rose bengal), cyanines (such as thiacarbocyanine, andoxacarbocyanine), merocyanines (such as merocyanine, andcarbomerocyanine), thiazines (such as thionine, methylene blue, andtoluidine blue), acridines (such as acridine orange, chloroflavin, andacriflavine), anthraquinones (such as anthraquinone), squaryliums (suchas squarylium), and coumarins (such as 7-diethylamino-4-methylcoumarin).

The sensitizer may be used singly or in a combination of two or morethereof.

The content of the photopolymerization initiator in the ink jet liquidcomposition according to the embodiment of the present disclosure ispreferably 0.1% by mass to 20.0% by mass, more preferably 0.5% by massto 18.0% by mass, and even more preferably 1.0% by mass to 15.0% by masswith respect to the total mass of the liquid composition. A case wherethe amount of the polymerization initiator added is in the above rangeis suitable from the viewpoint of excellent curability and reduction ofsticky feeling of the surface.

In addition, the content ratio (mass ratio) between the polymerizationinitiator and the polymerizable compound to be used in combination(polymerization initiator:polymerizable compound) is preferably 0.5:100to 30:100, more preferably 1:100 to 15:100, and even more preferably2:100 to 10:100, respectively.

<Vinyl Chloride-Vinyl Acetate Copolymer>

It is preferable that the ink jet liquid composition according to theembodiment of the present disclosure contains a vinyl chloride-vinylacetate copolymer (also referred to as a “specific copolymer”).

The vinyl chloride-vinyl acetate copolymer in the present disclosuredoes not have a polymerizable group.

The copolymerization ratio in the vinyl chloride-vinyl acetate copolymerin the present disclosure is not particularly limited, but from theviewpoint of ink jet jettability, the copolymerization amount of vinylchloride is preferably 70% by mass to 95% by mass, the copolymerizationamount of vinyl acetate is preferably 5% by mass to 30% by mass, thecopolymerization amount of vinyl chloride is more preferably 80% by massto 93% by mass, the copolymerization amount of vinyl acetate is morepreferably 7% by mass to 20% by mass, the copolymerization amount ofvinyl chloride is particularly preferably 80% by mass to 90% by mass,and the copolymerization amount of vinyl acetate is particularlypreferably 10% by mass to 20% by mass.

The weight-average molecular weight (Mw) of the vinyl chloride-vinylacetate copolymer is preferably 5,000 or more and 100,000 or less, morepreferably 10,000 or more and 70,000 or less, and even more preferably12,000 or more and 50,000 or less from the viewpoint of ink jetjettability.

As the vinyl chloride-vinyl acetate copolymer, a commercially availableproduct may be used.

Examples of the commercially available product include a vinylchloride-vinyl acetate copolymer manufactured by Wacker Chemie Gmbh, andSOLBIN CL, CNL, C5R, TA3, and TA5R manufactured by Nissin Chemical co.,ltd.

The vinyl chloride-vinyl acetate copolymer may be used singly or in acombination of two or more thereof.

The content of the vinyl chloride-vinyl acetate copolymer in the ink jetliquid composition according to the embodiment of the present disclosureis preferably 0.1% by mass or more and 10% by mass or less, morepreferably 0.5% by mass or more and 5% by mass or less, and particularlypreferably 1% by mass or more and 3% by mass or less with respect to thetotal mass of the liquid composition from the viewpoint of ink jetjettability and the abrasion resistance and the chemical resistance ofthe obtained cured film.

<Colorant>

In a case where the ink jet liquid composition according to theembodiment of the present disclosure is used for applications for an inkcomposition or the like, the ink jet liquid composition may contain acolorant, but it is preferable that the liquid composition does notcontain a colorant.

In the present disclosure, the expression “does not contain a colorant”means that a small amount of contamination or the like is allowed, andthe ink jet liquid composition does not completely contain the colorantor the content of the colorant is more than 0% by mass and 0.1% by massor less with respect to the total mass of the composition. In addition,in a case where the ink jet liquid composition is used for applicationsof a clear ink composition or the like, it is preferable that the inkjet liquid composition does not contain the colorant at all or thecontent of the colorant is more than 0% by mass and 0.05% by mass orless with respect to the total mass of the composition and it is morepreferable that the ink jet liquid composition does not contain thecolorant at all or the content of the colorant is more than 0% by massand 0.01% by mass or less with respect to the total mass of thecomposition.

The colorant is not particularly limited and pigments and oil-solubledyes which are excellent in weather fastness and rich in colorreproducibility are preferable. The colorant can be randomly selectedfrom known colorants such as soluble dyes and used. As the colorant, itis preferable to select a compound which does not function as apolymerization inhibitor from the viewpoint of not lowering thesensitivity of the curing reaction by active radiation.

The pigment is not particularly limited and can be selectedappropriately according to the purpose. Examples thereof include knownorganic pigments and inorganic pigments, and resin particles dyed with adye, commercially available pigment dispersions, and surface-treatedpigments (for example, a dispersion of a pigment in an insoluble resin,or the like, as a dispersion medium, or a pigment having a resin graftedon the surface) may be used.

Examples of these pigments include pigments described in, for example,“Pigment Dictionary”, edited by Seishiro Ito (2000), “Industrial OrganicPigments” edited by W. Herbst, K. Hunger, JP2002-012607A,JP2002-188025A, JP2003-026978A, and JP2003-342503A.

Examples of the organic pigments and inorganic pigments include yellowpigments, magenta pigments, cyan pigments, green pigments, orangepigments, brown pigments, violet pigments, black pigments and whitepigments.

The yellow pigments are pigments exhibiting yellow color, and examplesthereof include monoazo pigments such as C.I. Pigment Yellow 1 (FastYellow G and the like), and C.I. Pigment Yellow 74, disazo pigments suchas C.I. Pigment Yellow 12 (Disazo Yellow and the like), C.I. PigmentYellow 17, C.I. Pigment Yellow 97, C.I. Pigment Yellow 3, C.I. PigmentYellow 16, C.I. Pigment Yellow 83, C.I. Pigment Yellow 155, and C.I.Pigment Yellow 219, non-benzidine-based azo pigments such as C.I.Pigment Yellow 180, azo lake pigments such as C.I. Pigment Yellow 100(Tartrazine Yellow Lake and the like), condensed azo pigments such asC.I. Pigment Yellow 95 (Condensed Azo Yellow and the like), C.I. PigmentYellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 128, and C.I.Pigment Yellow 166, acid dye lake pigments such as C.I. Pigment Yellow115 (Quinoline Yellow Lake and the like), basic dye lake pigments suchas C.I. Pigment Yellow 18 (Thioflavine Lake and the like), anthraquinonepigments such as C.I. Pigment Yellow 24 (Flavanthrone Yellow and thelike), quinophthalone pigments such as C.I. Pigment Yellow 110(Quinophthalone Yellow and the like), isoindoline pigments such as C.I.Pigment Yellow 139 (Isoindoline Yellow and the like), pyrazolonepigments such as C.I. Pigment Yellow 60 (Pyrazolone Yellow and thelike), acetolone pigments such as C.I. Pigment Yellow 120, C.I. PigmentYellow 154, C.I. Pigment Yellow 167, C.I. Pigment Yellow 151, C.I.Pigment Yellow 175, C.I. Pigment Yellow 180, C.I. Pigment Yellow 181,C.I. Pigment Yellow 185, and C.I. Pigment Yellow 194, metal complex saltpigments such as C.I. Pigment Yellow 150, nitroso pigments such as C.I.Pigment Yellow 153 (Nickel Nitroso Yellow and the like), and metalcomplex salt azomethine pigments such as C.I. Pigment Yellow 117 (CopperAzomethine Yellow and the like).

The magenta pigments are pigments exhibiting red or magenta color, andexamples thereof include monoazo-based pigments such as C.I. Pigment Red3 (Toluidine Red and the like), B-naphthol pigments such as C.I. PigmentRed 1, C.I. Pigment Red 4, and C.I. Pigment Red 6, disazo pigments suchas C.I. Pigment Red 38 (Pyrazolone Red B and the like), azo lakepigments such as C.I. Pigment Red 53:1 (Lake Red C and the like), C.I.Pigment Red 57:1 (Brilliant Carmine 6B and the like), C.I. Pigment Red52:1, and C.I. Pigment Red 48 (B-oxynaththoic acid lake and the like),condensed azo pigments such as C.I. Pigment Red 144, C.I. Pigment Red166, C.I. Pigment Red 220, C.I. Pigment Red 214, C.I. Pigment Red 221,and C.I. Pigment Red 242 (Condensed Azo Red and the like), acid dye lakepigments such as C.I. Pigment Red 174 (Phloxine B Lake and the like),and the C.I. Pigment Red 172 (Erythrosine Lake and the like), basic dyelake pigments such as C.I. Pigment Red 81 (Rhodamine 6G′ Lake and thelike), anthraquinone-based pigments such as C.I. Pigment Red 177(Dianthraquiononyl Red and the like), thioindigo pigments such as C.I.Pigment Red 88 (Thioindigo Bordeaux and the like), perinone pigmentssuch as C.I. Pigment Red 194 (Perinone Red and the like), perylenepigments such as C.I. Pigment Red 149, C.I. Pigment Red 179, C.I.Pigment Red 178, C.I. Pigment Red 190, C.I. Pigment Red 224, and C.I.Pigment Red 123, quinacridone pigments such as C.I. Pigment Violet 19(unsubstituted quinacridone), C.I. Pigment Red 122, C.I. Pigment Red262, C.I. Pigment Red 207, and C.I. Pigment Red 209, isoindolinonepigments such as C.I. Pigment Red 180 (Isoindolinone Red 2BLT and thelike), alizarin lake pigments such as C.I. Pigment Red 83 (Madder Lakeand the like), naphtholone pigments such as C.I. Pigment Red 171, C.I.Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 185, and C.I.Pigment Red 208, naphthol AS-based lake pigments such as C.I. PigmentRed 247, naphthol AS pigments such as C.I. Pigment Red 2, C.I. PigmentRed 5, C.I. Pigment Red 21, C.I. Pigment Red 170, C.I. Pigment Red 187,C.I. Pigment Red 256, C.I. Pigment Red 268, and C.I. Pigment Red 269,and diketopyrrolopyrrole pigments such as C.I. Pigment Red 254, C.I.Pigment Red 255, C.I. Pigment Red 264, and C.I. Pigment Red 272.

The cyan pigments are pigments exhibiting blue or cyan color, andexamples thereof include disazo-based pigments such as C.I. Pigment Blue25 (Dianisidine Blue and the like), phthalocyanine pigments such as C.I.Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I.Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I.Pigment Blue 16 (Phthalocyanine Blue and the like), acid dye lakepigments such as C.I. Pigment Blue 24 (Peacock Blue Lake and the like),basic dye lake pigments such as C.I. Pigment Blue 1 (Victoria Pure BlueBO Lake and the like), anthraquinone-based pigments such as C.I. PigmentBlue 60 (Indanthrone Blue and the like), and alkali blue pigments suchas C.I. Pigment Blue 18 (Alkali Blue V-5:1).

The green pigments are pigments exhibiting green color, and examplesthereof include phthalocyanine pigments such as C.I. Pigment Green 7(Phthalocyanine Green), and C.I. Pigment Green 36 (PhthalocyanineGreen), and azo metal complex pigments such as C.I. Pigment Green 8, andC.I. Pigment Green 10.

The orange pigments are pigment exhibiting orange color, and examplesthereof include isoindoline-based pigments such as C.I. Pigment Orange66 (Isoindoline Orange), anthraquinone-based pigments such as C.I.Pigment Orange 51 (Dichloro Pyranthorone Orange), B-naphthol pigmentssuch as C.I. Pigment Orange 2, C.I. Pigment Orange 3, and C.I. PigmentOrange 5, naphthol AS pigments such as C.I. Pigment Orange 4, C.I.Pigment Orange 22, C.I. Pigment Orange 24, C.I. Pigment Orange 38, andC.I. Pigment Orange 74, isoindolinone pigments such as C.I. PigmentOrange 61, perinone pigments such as C.I. Pigment Orange 43, disazopigments such as C.I. Pigment Orange 15 and C.I. Pigment Orange 16,quinacridone pigments such as C.I. Pigment Orange 48, and C.I. PigmentOrange 49, acetolone pigments such as C.I. Pigment Orange 36, C.I.Pigment Orange 62, C.I. Pigment Orange 60, C.I. Pigment Orange 64, andC.I. Pigment Orange 72, and Pyrazolone pigments such as C.I. PigmentOrange 13, and C.I. Pigment Orange 34.

The brown pigments are pigments exhibiting brown color, and examplesthereof include naphtholone pigments such as C.I. Pigment Brown 25 andC.I. Pigment Brown 32.

The violet pigments are pigments exhibiting purple color, and examplesthereof include naphtholone pigments such as C.I. Pigment Violet 32,perylene pigments such as C.I. Pigment Violet 29, naphthol AS pigmentssuch as C.I. Pigment Violet 13, C.I. Pigment Violet 17, and C.I. PigmentViolet 50, and dioxazine pigments such as C.I. Pigment Violet 23 andC.I. Pigment Violet 37.

The black pigments are pigments exhibiting black color, and examplesthereof include carbon black such as MOGUL E, titanium black, indazinepigments such as and the C.I. Pigment Black 1 (Aniline Black), andperylene pigments such as C.I. Pigment Black 31, and C.I. Pigment Black32.

Examples of the white pigments include basic lead carbonate(2PbCO₃Pb(OH)₂, a so-called silver white), zinc oxide (ZnO, a so-calledzinc white), titanium oxide (TiO₂, a so-called titanium white), andstrontium titanate (SrTiO₃, a so-called a titanium strontium white).Inorganic particles used for a white pigment may be a simple substance,or may be complex particles with oxides of silicon, aluminum, zirconiumor titanium, or with organometallic compounds and an organic compound.

Among them, since titanium oxide has a low specific gravity as comparedwith other white pigments and has a high refractive index, is chemicallyand physically stable, and is excellent in the covering power andadhesion as a pigment, and further, the durability in acidic, alkalineand other environments, titanium oxide is suitably used. Other whitepigments (may be white pigments other than the above white pigments) maybe used together with titanium oxide in combination.

For the dispersion of the pigment, for example, dispersion apparatusessuch as a ball mill, a sand mill, an attritor, a roll mill, a jet mill,a homogenizer, a paint shaker, a kneader, an agitator, a HENSCHEL mixer,a colloid mill, an ultrasound homogenizer, a pearl mill, a wet-type jetmill, and the like can be suitably used.

In the present disclosure, a dispersant to be described later ispreferably added upon dispersion of the pigment.

In addition, upon dispersion of the pigment, if necessary, a synergistaccording to various pigments may be added as a dispersion aid. Thecontent of the dispersion aid in the liquid composition is preferably 1part by mass to 50 parts by mass with respect to 100 parts by mass ofthe pigment.

The dispersion medium used in a case where the pigment is dispersed inthe liquid composition is not particularly limited and can beappropriately selected according to the purpose. For example, thepolymerizable compound with a low molecular weight may be used as thedispersion medium, or a solvent is used as the dispersion medium.However, since the ink jet liquid composition according to theembodiment of the present disclosure is a radiation curable-typepolymerizable composition and, for example, the liquid composition iscured after the polymerizable composition is applied onto a recordingmedium, a solvent-free dispersion medium containing no solvent ispreferable. This is because in a case where a solvent remains in thecured product, solvent resistance is deteriorated or problems associatedwith a volatile organic compound (VOC) of the remaining solvent.Therefore, from the viewpoint of improving the dispersion suitabilityand handleability of the liquid composition, it is preferable that thepolymerizable compounds are used as the dispersion medium and that apolymerizable compound with the lowest viscosity is selected from amongthese polymerizable compounds.

The average particle diameter of the pigment is not particularly limitedand can be appropriately selected according to the purpose. However,since the color developability improves with the decrease in particlediameter, the average particle diameter is preferably about 0.01 μm to0.4 μm and more preferably 0.02 μm to 0.2 μm. In addition, a particlediameter of 3 μm or less is preferable and 1 μm or less is morepreferable as the maximum particle diameter of the pigment. The particlediameter of the pigment can be adjusted by appropriately selecting thepigment, dispersant, and dispersion medium and by setting appropriatedispersion conditions and filtration conditions. By controlling theparticle diameter of the pigment, it is possible to prevent a head ofnozzle from clogging and maintain preservation stability, transparency,and curing sensitivity.

The particle diameter of the pigment can be measured by a knownmeasurement method. Specifically, the measurement can be performed by acentrifugal sedimentation light transmission method, an X-raytransmission method, a laser diffraction and scattering method, and adynamic light scattering method.

The colorant may be used singly or in combination of two or morethereof.

In a case where the ink jet liquid composition according to theembodiment of the present disclosure contains the colorant, the contentof the colorant in the ink jet liquid composition is appropriatelyselected according to the color and the purpose of use, but ispreferably 0.01% by mass to 20% by mass with respect to the total massof the composition.

<Dispersant>

The ink jet liquid composition according to the embodiment of thepresent disclosure may contain a dispersant. Particularly, in a case ofusing a pigment, since the pigment is stably dispersed in thecomposition, it is preferable to contain a dispersant. The dispersant ispreferably a polymer dispersant. The term “polymer dispersant” in thepresent disclosure means a dispersant having a weight-average molecularweight of 1,000 or more. Examples of the polymer dispersant includeDISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106,DISPERBYK-11, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163,DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168,DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, and DISPERBYK-182(manufactured by BYK Chemie GmbH)); EFKA4010, EFKA4046, EFKA4080,EFKA5010, EFKA5207, EFKA5244, EFKA6745, EFKA6750, EFKA7414, EFKA745,EFKA7462, EFKA7500, EFKA7570, EFKA7575, EFKA7580, and EFKA7701(manufactured by EFKA Additives Co., Ltd.); DISPERSE AID 6, DISPERSE AID8, DISPERSE AID 15, and DISPERSE AID 9100 (manufactured by San NopcoCo., Ltd.); various SOLSPERSE dispersants such as SOLSPERSE 3000, 5000,9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, 32000,36000, 39000, 41000, and 71000 (manufactured by Noveon, Inc.); ADEKAPLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87,P94, L101, P103, F108, L121, and P-123 (manufactured by ADEKA Ltd.),IONETTO S-20 (manufactured by Sanyo Chemical Industries, Ltd.);DISPARLON KS-860, 873SN, and 874 (polymer dispersant), #2150 (aliphaticpolyvalent carboxylic acid), and #7004 (polyether ester type)(manufactured by Kusumoto Kasei Co., Ltd.).

The dispersant may be used singly or in combination of two or morethereof.

The content of the dispersant in the liquid composition according to theembodiment of the present disclosure is appropriately selected accordingto the purpose of use and is preferably 0.05% by mass to 10% by masswith respect to the total mass of the liquid composition.

<Other Components>

To the ink jet liquid composition according to the embodiment of thepresent disclosure, in addition to the above-described components, ifnecessary, known additives such as a polymerization inhibitor, anultraviolet absorber, an antioxidant, an antifading agent, a surfaceconditioner, a leveling agent, a matting agent, a wax, an antifoamingagent, a pH adjuster, a charge imparting agent, a disinfectant, apreservative, a deodorant, a charge controlling agent, a wetting agent,an antiskinning agent, a fragrance, and a pigment derivative may beadded as an arbitrary component.

The ink jet liquid composition according to the embodiment of thepresent disclosure preferably contains a polymerization inhibitor fromthe viewpoint of improving storability and suppressing clogging of anink jet head.

The content of the polymerization inhibitor is preferably 200 ppm to20,000 ppm with respect to the total mass of the composition.

Examples of the polymerization inhibitor include nitroso-basedpolymerization inhibitors, hindered amine-based polymerizationinhibitors, hydroquinone, benzoquinone, p-methoxy phenol, TEMPO, TEMPOL,and CUPERON A1.

<Physical Properties of Ink Jet Liquid Composition>

The viscosity of the ink jet liquid composition according to theembodiment of the present disclosure at 25° C. is preferably 1 mPa·s to40 mPa·s, and more preferably 3 mPa·s to 30 mPa·s.

In addition, the viscosity at the temperature at the time of ink jetting(preferably 25° C. to 80° C., more preferably 25° C. to 50° C.) ispreferably 1 mPa·s to 30 mPa·s and more preferably 3 mPa·s to 25 mPa·s.The ink jet liquid composition that can be used in the presentdisclosure preferably has the compositional ratio appropriately adjustedsuch that the viscosity is set to be in the above-described ranges. Itis possible to inhibit bleeding when a liquid droplet of the liquidcomposition lands.

The measurement method of the viscosity is not particularly limited;however, preferable examples include a method using a model RE80viscometer manufactured by Toki Sangyo Co., Ltd. The model RE80 typeviscometer is a conical rotor and flat plate type viscometercorresponding to an E-type, and measurement is preferably performed at arotation speed of 10 rpm using rotor code No. 1 as a rotor. Herein,measurement is preferably performed by changing the rotation speed to 5rpm, 2.5 rpm, 1 rpm, 0.5 rpm and the like if necessary for those havinga high viscosity higher than 60 mPa·s.

In addition, the surface tension of the ink jet liquid compositionaccording to the embodiment of the present disclosure at 25° C. ispreferably 18 mN/m or more and 50 mN/m or less, and more preferably 20mN/m or more and 40 mN/m or less from the viewpoint of appropriatenessof liquid droplet jetting by the ink jet.

In addition, the surface tension of the ink jet liquid compositionaccording to the embodiment of the present disclosure is a valuemeasured at a liquid temperature of 25° C. with the Wilhelmy methodusing a generally used surface tensiometer (for example, a CBVP-Zsurface tensiometer, manufactured by Kyowa Interface Science Co., Ltd.,or the like).

(Ink Jet Recording Method)

An ink jet recording method according to an embodiment of the presentdisclosure includes a step of applying the ink jet liquid compositionaccording to the embodiment of the present disclosure to a base materialby an ink jet recording head.

The base material is preferably a base material having a concave-convexshape in at least a part of the surface and more preferably leather fromthe viewpoint of further exerting the effects of ink jet liquidcomposition according to the embodiment of the present disclosure.

In the step of the applying, the liquid composition may be directlyapplied to the base material or a layer such as a decorative layer maybe provided to the base material and the liquid composition may beapplied to the layer.

The ink jet jetting condition and the jetting amount in the step of theapplying are not particularly limited and may be appropriately selectedaccording to the composition and physical properties of the liquidcomposition to be used, the base material, and the like.

In addition, a printed material according to the embodiment of thepresent disclosure is a printed material having a cured product obtainedby curing the ink jet liquid composition according to the embodiment ofthe present disclosure, and is preferably a printed material on whichrecording is performed by the ink jet recording method according to theembodiment of the present disclosure.

In the ink jet recording method according to the embodiment of thepresent disclosure, an ink jet recording apparatus to be described laterin detail can be used.

The ink jet recording apparatus that can be used in the ink jetrecording method according to the embodiment of the present disclosureis not particularly limited and, a known ink jet recording apparatuscapable of achieving a desired resolution can be arbitrarily selectedand used. That is, any ink jet recording apparatus can jet the liquidcomposition to the base material in the ink jet recording methodaccording to the embodiment of the present disclosure as long as the inkjet recording apparatus is a known ink jet recording apparatus includingcommercially available products.

Examples of the ink jet recording apparatus according to the embodimentof the present disclosure include apparatuses including ink supplysystems, temperature sensors, and active radiation sources.

The ink supply system, for example, is formed of a source tank includingthe liquid composition according to the embodiment of the presentdisclosure, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo type ink jet head. The piezo type inkjet head can perform driving so as to enable jetting multi-size dots ofpreferably 1 pl to 100 pl, and more preferably 8 pl to 30 pl at aresolution of preferably 320×320 dpi to 4,000×4,000 dpi, more preferably400×400 dpi to 1,600×1,600 dpi, and even more preferably 720×720 dpi.The term dpi (dot per inch) used in the present disclosure representsthe number of dots per 2.54 cm.

As described above, for the liquid composition according to theembodiment of the present disclosure, since it is preferable that thejetted liquid composition is set to a constant temperature, it ispreferable that means for stabilizing the liquid composition temperatureis provided in the ink jet recording apparatus. As sites made a constanttemperature, all of the pipe system and members from the ink tank (theintermediate tank, in a case where there is an intermediate tank) to thenozzle emission surface become targets. That is, insulation and heatingcan be performed from the ink supply tank to the ink jet head portion.

The temperature control method is not particularly limited; however, forexample, it is preferable to provide a plurality of temperature sensorsat sites at each pipe and perform heating control according to the flowrate of the liquid composition and the environmental temperature. Thetemperature sensors can be provided in the vicinity of the ink supplytank and the nozzles of the ink jet head. In addition, the head unit tobe heated is preferably thermally blocked or insulated such that theapparatus main body is not influenced by the temperature from theoutside air. In order to shorten the printer startup time required forheating, or in order to reduce the thermal energy loss, it is preferableto provide insulation from other sites and to decrease the heat capacityof the entire heating unit body.

In addition, it is preferable to keep the temperature of the liquidcomposition during jetting as constant as possible. The control range ofthe temperature of the liquid composition during jetting is set topreferably ±5° C. of a set temperature, more preferably ±2° C., and evenmore preferably ±1° C. is appropriate.

In addition, it is preferable that the ink jet recording methodaccording to the embodiment of the present disclosure further includes astep of drying the ink jet liquid composition on the base material byapplying heat; and a step of curing the ink jet liquid composition byirradiating the ink jet liquid composition with active radiation.

In the ink jet recording method according to the embodiment of thepresent disclosure, the liquid composition may be dried by air or may bedried by applying heat, but is preferably dried by applying heat.

The drying temperature in the step of the drying is not particularlylimited and may be appropriately set according to the boiling point ofthe organic solvent in the liquid composition. The base materialtemperature is preferably 30° C. or higher and 90° C. or lower and morepreferably 50° C. or higher and 80° C. or lower.

Next, the irradiation with active radiation will be described.

The dried liquid composition on the base material is cured by beingirradiated with active radiation. This is because the polymerizationinitiator included in the liquid composition according to the embodimentof the present disclosure generates polymerization initiating species,such as radicals by decomposing due to irradiation with activeradiation, and the polymerization reaction of the polymerizable compoundis started and promoted by the function of the initiating species. Atthis time, in a case where a sensitizer is present along with apolymerization initiator in the liquid composition, the sensitizer inthe system absorbs active radiation and enters an excited state, thedecomposition of the polymerization initiator is promoted by the contactwith the sensitizer, and a curing reaction with a higher sensitivity canbe attained.

Here, the active radiation used can be an α-ray, a γ-ray, an electronbeam, an X-ray, an ultraviolet (UV) ray, visible light or infraredlight. The peak wavelength of the active radiation also depends on theabsorption characteristics of the sensitizer. However, the peakwavelength is preferably 200 nm to 600 nm, more preferably 300 nm to 450nm, and even more preferably 320 nm to 420 nm, and the active energy rayis particularly preferably an ultraviolet ray with a peak wavelength ina range of 340 nm to 400 nm.

In addition, the polymerization initiation system of the liquidcomposition according to the embodiment of the present disclosure hassufficient sensitivity even with a low output active energy ray.Accordingly, curing is suitably performed with an exposure surfaceilluminance of preferably 10 mW/cm² to 4,000 mW/cm², and more preferably20 mW/cm² to 2,500 mW/cm².

As the active radiation source, a mercury lamp, a gas or solid-statelaser, or the like is mainly used, and a metal halide lamp is widelyknown. However, currently, the current move toward becoming mercury freeis strongly desired from the viewpoint of environmental protection, andreplacement with GaN-based semiconductor ultraviolet light emittingdevices is industrially and environmentally extremely effective.Further, LED (UV-LED) and LD (UV-LD) are small size and low cost, andhave long service life and high efficiency, and are anticipated as aphotocuring type ink jet light source.

In addition, it is possible to use light emitting diodes (LED) and laserdiodes (LD) as active radiation sources. In particular, in a case wherean ultraviolet source is required, an ultraviolet LED and an ultravioletLD can be used. For example, Nichia Corporation has brought anultraviolet LED to market having a wavelength with a main emissionspectrum between 365 nm and 420 nm. Furthermore, in a case where an evenshorter wavelength is needed, the specification of U.S. Pat. No.6,084,250A discloses an LED capable of emitting active radiationcentered between 300 nm and 370 nm. In addition, other ultraviolet LEDsare available and can emit radiation of different ultraviolet ray bands.In the present disclosure, a UV-LED is a particularly preferable activeenergy ray source, and particularly preferable is a UV-LED having a peakwavelength of 340 nm to 400 nm.

In addition, the maximum illuminance on the recording medium of the LEDis preferably 10 mW/cm² to 2,000 mW/cm², more preferably 20 mW/cm² to1,000 mW/cm², and particularly preferably 50 mW/cm² to 800 mW/cm².

The ink jet liquid composition according to the embodiment of thepresent disclosure is suitably irradiated with such active radiation forpreferably 0.01 seconds to 120 seconds and more preferably 0.1 secondsto 90 seconds.

The irradiation conditions of the active radiation and the basicirradiation method are disclosed in JP1985-132767A (JP-S60-132767A).

Further, curing may be completed using another light source that is notdriven. WO99/054415A as an irradiation method, a method using an opticalfiber, and a method of directing a collimated light source to a mirrorsurface, which is provided on the side surface of a head unit, toirradiate a recorded area with UV light. The above-described curingmethods can be applied to the ink jet recording method according to theembodiment of the present disclosure.

Among these, as the ink jet recording method according to the embodimentof the present disclosure, an ink jet recording method including a stepof preparing a base material having a decorative layer formed thereon, astep of applying the ink jet liquid composition according to theembodiment of the present disclosure not containing a colorant to thedecorative layer by an ink jet recording head, a step of drying the inkjet liquid composition on the decorative layer by applying heat, and astep of curing the ink jet liquid composition by irradiating the ink jetliquid composition with an ultraviolet ray, in which the base materialhaving the decorative layer formed thereon has a concave-convex shape inat least a part of a surface is preferably used.

The decorative layer may be formed using the liquid compositionaccording to the embodiment of the present disclosure as a coloring inkcomposition or may be formed using a known ink composition.

Among these, an embodiment in which both the decorative layer and theovercoat formed on the decorative layer are formed by the ink jet liquidcomposition according to the embodiment of the present disclosure ispreferable. The above embodiment is particularly preferable for adecorative layer and an overcoat provided on a base material having aconcave-convex shape in at least a part of the surface thereof.

By forming an overcoat on the decorative layer using the liquidcomposition according to the embodiment of the present disclosure, evenin a case where a known ink composition is used, abrasion resistance,bendability, and chemical resistance are excellent.

In addition, as the ink jet recording method according to the embodimentof the present disclosure, an ink jet recording method including a stepof applying the ink jet liquid composition containing a colorantaccording to the embodiment of the present disclosure to a base materialby an ink jet recording head, a step of drying the ink jet liquidcomposition on the base material by applying heat, a step of curing theink jet liquid composition by irradiating the ink jet liquid compositionwith an ultraviolet ray to form a decorative layer, a step of applyingthe ink jet liquid composition according to the embodiment of thepresent disclosure not containing a colorant to the decorative layer byan ink jet recording head, a step of drying the ink jet liquidcomposition on the decorative layer by applying heat, and a step ofcuring the ink jet liquid composition by irradiating the ink jet liquidcomposition with an ultraviolet ray is preferable, and an ink jetrecording method in which the base material has a concave-convex shapein at least a part of the surface thereof is more preferable.

As the base material, not only a base material having a concave-convexshape in at least a part of the surface of the above-mentioned leatheror the like, but also papers such as ordinary uncoated paper and coatedpaper, various nonabsorbent resin materials used for so-called softpackaging and resin films formed by molding the resins materials in afilm form can also be used.

Examples of the various plastic films include a polyethyleneterephthalate (PET) film, a biaxially oriented polystyrene (OPS) film, abiaxially oriented polypropylene (OPP) film, a biaxially oriented nylon(ONy) film, a polyvinyl chloride (PVC) film, a polyethylene (PE) film,and a cellulose triacetate (TAC) film.

In addition, examples of plastics that can be used as the base materialinclude polycarbonate, an acrylic resin, anacrylonitrile-butadiene-styrene (ABS) copolymer, polyacetal, polyvinylalcohol (PVA), and rubbers. Further, metals and glasses can be used asthe recording medium.

EXAMPLES

Hereinafter, the present invention will be more specifically describedbased on examples, but the present disclosure is not limited to theexamples. Herein, unless otherwise specified, “part” and “%” are basedon mass.

<L2/L1 in Base Material>

The L2/L1 in the base material was measured using a shape analysis lasermicroscope (VK-X250/260, manufactured by Keyence Corporation).

Hereinafter, the details of various components used in Examples andComparative Examples are shown.

-   -   Cyan pigment (PB15:4, C.I. Pigment Blue 15:4, HELIOGEN BLUE D        7110 F, manufactured by BASF SE)    -   Magenta pigment (mixed quinacridone, CINQUASIA MAGENTA L 4540,        manufactured by BASF SE)    -   Yellow pigment (PY155, C.I. Pigment Yellow 155, INK JET YELLOW        4GC, manufactured by Clarinat)    -   Black pigment (carbon black, MOGUL E, manufactured by CABOT)        -   Dispersant (Sol32000, SOLSPERSE 32000, manufactured by The            Lubrizol Corporation)

The details of the organic solvents used in Examples and ComparativeExamples are shown in Table 1.

TABLE 1 Boiling Compound name point (° C.) Manufacturer 3-Methoxybutylacetate 172 Tokyo Chemical Industry Co., Ltd. Triethylene glycolmonobutyl 278 Tokyo Chemical Industry ether (TEGMBE) Co., Ltd.Diethylene glycol dimethyl 188 Tokyo Chemical Industry ether (DEGDEE)Co., Ltd.

The details of the urethane (meth)acrylate oligomers (oligomers) used inExamples and Comparative Examples are shown in Table 2.

TABLE 2 Trade name Manufacturer Functional number Mw CN9001 SartomerCompany Inc. Bifunctional 3,250 SHIKO The Nippon SyntheticHexafunctional 1,400 UV-7600B Chemical Industry Co., Ltd. SHIKO TheNippon Synthetic Bifunctional 5,000 UV-3310B Chemical Industry Co., Ltd.SHIKO The Nippon Synthetic Trifunctional 2,400 UV-7550B ChemicalIndustry Co., Ltd.

The details of the vinyl chloride-vinyl acetate copolymers used inExamples and Comparative Examples are shown in Table 3.

TABLE 3 Vinyl Vinyl Vinyl chloride- chloride acetate vinyl acetate (% by(% by copolymer mass) mass) Mw Manufacturer vinnol H14/36 85.6 14.416,000 Wacker Chemie AG vinnol H11/59 90.5 9.5 43,000 Wacker Chemie AG

-   -   Polymerization inhibitor (UV 22, Irgastab (registered trademark)        UV-22,        Poly[oxy(methyl-1,2-ethanediyl)]-α,α′,α″-1,2,3-propanetriyltris[-[(1-oxo-2-propen-1-yl)oxy]-2,6-bis(1,1-dimethylethyl)-4-(phenylenemethylene)cyclohexa-2,5-dien-1-one],        manufactured by BASF SE)    -   Polymerization inhibitor (UV 12, nitroso-based polymerization        inhibitor, tirs(N-nitroso-N-phenylhydroxylamine) aluminum salt,        FLORSTAB UV12, manufactured by Kromachem Co., Ltd.)    -   Photopolymerization initiator (Irg819,        bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, IRGACURE        (registered trademark) 819, manufactured by BASF SE)        Photopolymerization initiator (Irg2959, 1-[4-(2-hydroxyethoxy)        phenyl]-2-hydroxy-2-methyl-1-propane-1-one, IRGACURE (registered        trademark) 2959, manufactured by BASF SE)    -   Monomer (PEA, 2-phenoxyethyl acrylate, SR339C, manufactured by        Sartomer Company Inc.)    -   KP109 (50% sol.) (50% by mass propylene glycol monomethyl ether        solution of polyether-modified siloxane compound, manufactured        by Shin-Etsu Chemical Co., Ltd., Mw 12,000, content of siloxane        structure: 29% by mass)    -   KP368 (polyether-modified siloxane compound, manufactured by        Shin-Etsu Chemical Co., Ltd., Mw 7,000, content of siloxane        structure: 90% by mass or more)    -   KP306 (polyether-modified siloxane compound, manufactured by        Shin-Etsu Chemical Co., Ltd., Mw 12,000, content of siloxane        structure: 25% by mass)    -   KP341 (polyether-modified siloxane compound, manufactured by        Shin-Etsu Chemical Co., Ltd., Mw 11,000, content of siloxane        structure: 15% by mass)    -   KF-96H-10,000 CS (polyether-modified siloxane compound,        manufactured by Shin-Etsu Chemical Co., Ltd., Mw70,000, content        of siloxane structure: 20% by mass or more)    -   KF-96H-30,000 CS (polyether-modified siloxane compound,        manufactured by Shin-Etsu Chemical Co., Ltd., Mw 90,000, content        of siloxane structure: 20% by mass or more)    -   KF-96H-100,000 CS (polyether-modified siloxane compound,        manufactured by Shin-Etsu Chemical Co., Ltd., Mw 100,000,        content of siloxane structure: 20 by mass or more)    -   BYK-UV 3500 (polyether modified polydimethylsiloxane,        manufactured by BYK Chemie GmbH, Mw 3,500, content of siloxane        structure: 30% by mass or more)    -   BYK 331 (polyether-modified polydimethylsiloxane, manufactured        by BYK Chemie GmbH, Mw 2,500, content of siloxane structure: 10%        by mass)    -   Efka SL 3210 (polyether-modified siloxane compound, manufactured        by Efka Chemicals, Mw 1,500, content of siloxane structure: 9%        by mass)    -   KP105 (30% sol.) (30% by mass propylene glycol monomethyl ether        solution of polyol-modified siloxane compound, manufactured by        Shin-Etsu Chemical Co., Ltd.)    -   MEGAFACE RS-72-K (40% sol.) (40% by mass methyl isobutyl ketone        solution of fluorine-based surfactant, manufactured by DIC        Corporation)

Examples 1 to 29 and Comparative Examples 1 to 11

<Preparation of Pigment Dispersion>

The compositions other than the pigments shown in Table 4 were mixed andstirred (10 to 15 minutes, 2,000 to 3,000 rpm/min) with a mixermanufactured by SILVERSON Co., Ltd. to obtain a homogenous colorlessliquid (diluted solution of dispersant). The pigments were added to thecolorless liquid (diluted solution of dispersant), and further stirredwith the mixer (10 to 20 minutes, 2,000 to 3,000 rpm/min) to obtain 500parts of a homogenous preliminary dispersion liquid. Thereafter, adispersion process was performed using a circulation bead mill device(SL-012C1) manufactured by EIGER Corp. Dispersion was performed underdispersion conditions in which 200 parts of zirconia beads with adiameter of 0.65 mm were charged, and the circumferential speed was setto 15 m/s. The dispersion time was set to 1 to 6 hours.

TABLE 4 Cyan Magenta Yellow Black pigment pigment pigment pigment millbase mill base mill base mill base Pigment PB15:4 Mixed PY155 Carbonblack quinacridone 30% by mass 30% by mass 30% by mass 30% by massDispersant Sol32000 Sol32000 Sol32000 Sol32000 10% by mass 15% by mass10% by mass 10% by mass DEGDEE 60% by mass 55% by mass 60% by mass 60%by mass

<Preparation of Coloring Liquid Composition>

The composition shown in Table 5 was mixed and stirred using a mixermanufactured by SILVERSON Machines, Inc. (10 to 15 minutes, 2,000 to3,000 rotations/min) to prepare a homogenous coloring liquidcomposition. This composition was used as a coloring liquid compositionfor Pattern 2 described later.

TABLE 5 Coloring liquid composition C1 M1 Y1 K1 Organic solvent3-Methoxybutyl 79.9 74.7 75.9 78.4 acetate Oligomer CN9001 7 7 7 7 Resinvinnol H14/36 3 3 3 3 Polymerization UV22 1 1 1 1 inhibitorPhotopolymerization Irg819 2 2 2 2 initiator Irg2959 1 1 1 1 SurfactantBYK 331 0.1 0.1 0.1 0.1 Cyan pigment mill base 6 — — — Magenta pigmentmill base — 11.2 — — Yellow pigment mill base — — 10 — Black pigmentmill base — — — 7.5

<Preparation of Ink Jet Liquid Composition>

Each compound and the like were mixed at the composition in each ofTables 6 to 9 shown below and stirred (10 to 15 minutes, 2,000 to 3,000rpm/min), with a mixer manufactured by SILVERSON Co., Ltd., to obtain ahomogenous ink jet liquid composition.

<Ink Jet Recording Method>

To an ink jet printer (KEGON) manufactured by Afit Corporation, a rubberheater (SR100, manufactured by ThreeHigh Co., Ltd.) and an ultraviolet(UV) irradiation apparatus (Vzero, manufactured by IntegrationTechnology) were attached. The output of the rubber heater was set suchthat the temperature of the base material could be increased to about60° C. In addition, the time from ink jet jetting to UV exposurecorresponded to the drying time of the liquid droplet and the transferspeed (5 m/min to 25 m/min) and the timing of opening or closing the UVshutter were adjusted such that the time was set to 10 seconds.

Printing was carried out with the configuration of two patterns. Eachconfiguration is as shown below.

—Printing Pattern 1 (Single Layer)—

By jetting the coloring liquid composition from an ink jet head heatedto 35° C., printing was performed on the base material (unless otherwisespecified, PVC leather (ARES YP606, manufactured by YAMAPLAS CO., LTD.,polyvinyl chloride synthetic leather, L2/L1=1.33) was used). At thistime, the image density was set to 1,200 dpi×600 dpi and the amount ofthe coloring liquid compositions applied (total amount of all colors) tothe base material was set to 20 g/m².

After the printing, the temperature was raised to 60° C. (base materialtemperature) by a rubber heater. The drying time was set to 60 seconds.

After drying, exposure was performed in an irradiation amount of 3,000mJ/cm² by a UV exposure machine to form a decorative layer.

—Printing Pattern 2—

By jetting the coloring liquid composition from an ink jet head heatedto 35° C., printing was performed on the base material (unless otherwisespecified, PVC leather (ARES YP606, manufactured by YAMAPLAS CO., LTD.,polyvinyl chloride synthetic leather, L2/L1=1.33) was used). At thistime, the image density was set to 1,200 dpi×600 dpi and the amount ofthe coloring liquid compositions applied (total amount of all colors) tothe base material was set to 20 g/m².

After the printing, the temperature was raised to 60° C. (base materialtemperature) by a rubber heater. The drying time was set to 60 seconds.

After drying, exposure was performed in an irradiation amount of 3,000mJ/cm² by a UV exposure machine to form a decorative layer.

A transparent liquid composition was jetted from the ink jet head heatedto 35° C. to this decorative layer. At this time, the image density wasset to 1,200 dpi×600 dpi and the amount of the transparent liquidcompositions applied to the base material was set to 10 g/m².

After the jetting, the temperature was raised to 60° C. (base materialtemperature) by a rubber heater. The drying time was set to 10 seconds.

After drying, exposure was performed in an irradiation amount of 3,000mJ/cm² by a UV exposure machine to form a protective layer.

1. Printing of Printing Pattern 1 with Coloring Liquid Composition Eachliquid composition shown in Table 8 or 9 was introduced into the ink jetprinter and the pattern 1 was printed.

Each of rectangular solid images of 20 cm×12 cm was printed to form acured image. The abrasion resistance, bendability, and chemicalresistance were evaluated using the cured image based on the evaluationstandards described later. The evaluation results are collectively shownin Table 8 or 9.

2. Printing of Printing Pattern 2 with Transparent Liquid Composition

Each liquid composition shown in Tables 6 to 9 was introduced into theink jet printer and the pattern 2 was printed. As the coloring liquidcomposition, a set of C1, M1, Y1, and K1 was used. A yellow solid imageof a size of 20 cm×12 cm was printed and a base material having adecorative layer formed thereon was prepared. Each of the transparentliquid compositions shown in Tables 6 to 9 was used as a transparentliquid composition to form a protective layer on the decorative layer.The abrasion resistance, bendability, and chemical resistance wereevaluated for the prepared samples according to the following evaluationstandards.

The evaluation results are collectively shown in Tables 6 to 9.

<Evaluation>

(Abrasion Resistance)

Using a gakushin type tester (manufactured by Suga Test Instruments Co.,Ltd.), a certain number of times of abrasion was carried out on theabove cured image while applying a load of 200 g by dried cotton (whitecloth for test: cotton (Kanakin No. 3, purchased from Japan StandardAssociation)). During this period, the number of times of abrasion untilscratches were visually recognized on the cured image was recorded andthe abrasion resistance of the cured image was evaluated according tothe following evaluation standards. 3 points or higher in the followingevaluation standards are considered as a pass.

—Evaluation Standards of Abrasion Resistance—

5 points: No scratches were generated even at 2,000 times of abrasion.

4 points: Scratches were generated at 1,000 times or more and less than2,000 times of abrasion.

3 points: Scratches were generated at 500 times or more and less than1,000 times of abrasion.

2 points: Scratches were generated at 100 times or more and less than500 of abrasion.

1 point: Scratches were generated at less than 100 times of abrasion.

(Bendability)

Using a bending tester (Flexiometer, manufactured by Yasuda SeikiSeisakusho, Ltd.), a certain number of times of bending was performed onthe base material on which the cured image was formed. During thisperiod, the number of times until cracks were visually recognized in thecured image was recorded and the bendability of the cured image wasevaluated according to the following evaluation standards. 3 points orhigher in the following evaluation standards are considered as a pass.

—Evaluation Standards of Bendability—

5 points: No cracks were generated even at 20,000 times of bending.

4 points: Cracks were generated at 10,000 times or more and less than20,000 times of bending.

3 points: Cracks were generated at 5,000 times or more and less than10,000 of bending.

2 points: Cracks were generated at 1,000 times or more and less than5,000 times of bending.

1 point: Cracks were generated at less than 1,000 of times of bending.

(Chemical Resistance)

Using a gakushin type tester (manufactured by Suga Test Instruments Co.,Ltd.), a certain number of times of abrasion was carried out on theabove cured image, while applying a load of 400 g by cotton impregnatedwith ethanol (white cloth for test: cotton (Kanakin No. 3, purchasedfrom Japan Standard Association)). During this period, the cured imagewas peeled off, the number of times until surface of the base materialwas visually recognized was recorded and the chemical resistance of thecured image was evaluated according to the following evaluationstandards. 3 points or higher in the following evaluation standards areconsidered as a pass.

—Evaluation Standards of Chemical Resistance—

5 points: The surface of the base material was not visually recognizedeven at 200 times of abrasion.

4 points: The surface of the base material was visually recognized at100 times or more and less than 200 times of abrasion.

3 points: The surface of the base material was visually recognized at 50times or more and less than 100 times of abrasion.

2 points: The surface of the base material was visually recognized at 10times or more and less than 50 of abrasion.

1 point: The surface of the base material was visually recognized atless than 10 times of abrasion.

(Adhesiveness)

The cured image was subjected to a cross cut test according to JIS K5066-5-6: 1992. The operation (hereinafter, referred to as “peelingoperation”) until the tape was attached to the cross-cut portion of thecured image and was peeled off was performed three times. During thistime, the portion subjected to the peeling operation was visuallyobserved, and the adhesiveness of the cured image was evaluatedaccording to the following evaluation standards. 3 points or higher inthe following evaluation standards are considered as a pass.

—Evaluation Standards of Adhesiveness—

5 points: The cured image was not damaged by three peeling operations.

4 points: The cured image was damaged by the third peeling operation.

3 points: The cured image was damaged by the second peeling operation.

2 points: The cured image was damaged by the first peeling operation.(however, the image was not peeled off).

1 point: The cured image was damaged and peeled off by the first peelingoperation.

(Ink Jet (IJ) Jetting Stability)

Under the same solid image printing conditions except that the basematerial was changed to an A3 size recording sheet (GASAI, ink jetphotographic printing paper, manufactured by Fujifilm Corporation),continuous solid image printing was performed on 40 recording sheet.Hereinafter, a recording sheet on which a solid image is printed isreferred to as a “sample”. 40 samples were visually observed and thenumber of samples in which nozzle missing (that is, an image defect dueto nozzle jetting failure) was confirmed in the solid image wasexamined. Based on this result, ink jet jetting stability was evaluatedaccording to the following evaluation standards. 3 points or higher inthe following evaluation standards are considered as a pass.

—Evaluation Standards of Ink Jet Jetting Stability—

5 points: Number of samples in which nozzle missing is confirmed is 0.

4 points: Number of samples in which nozzle missing is confirmed is 1.

3 points: Number of samples in which nozzle missing is confirmed is 2.

2 points: Number of samples in which nozzle missing is confirmed is 3.

1 point: Number of samples in which nozzle missing is confirmed is 4 ormore.

TABLE 6 Example 1 2 3 4 5 6 7 8 9 10 Printing pattern 2 2 2 2 2 2 2 2 22 Solvent 3-Methoxybutyl acetate 82 81 80 86 83.5 82.5 82.5 82 82 82Oligomer CN9001 (bifunctional, Mw 3,250) 5 5 5 4 4 4 5 5 5 5 SHIKOUV-7600B (hexafunctional, 5 5 5 4 4 4 5 5 5 5 Mw 1,400) Resin VinnolH14/36 2 2 2 1 1 1 2 2 2 2 Polymer- UV12 1 1 1 1 1 1 1 1 1 1 izationinhibitor Photopoly- Irg819 3 3 3 2 2 2 3 3 3 3 merization Irg2959 1 1 11 1 1 1 1 1 1 initiator Polyether- KP109 (50% sol.) (SiO content: 1 2 31 3.5 4.5 0.5 — — — modified 29% by mass, Mw 12,000) siloxane KP368 (SiOcontent: 90% by mass — — — — — — — 1 — — compound or more, Mw 7,000)KP306 (SiO content: 25% by mass, — — — — — — — — 1 — Mw 12,000) KP341(SiO content: 15% by mass, — — — — — — — — — 1 Mw 11,000) Total (partsby mass) 100 100 100 100 100 100 100 100 100 100 Content ofpolyether-modified siloxane compound 3 6 9 4 12 15 1 6 6 6 with respectto total solid content (% by mass) Content ratio of polymerizablecompound with 20 10 6.7 16 4.6 3.6 40 10 10 10 respect to parts by massof polyether-modified siloxane compound 1 (parts by mass) Base Abrasionresistance 5 5 3 5 3 3 4 5 5 3 material: Bendability 5 5 5 5 5 5 5 5 5 5ARES YP606 Chemical resistance 5 5 4 5 4 3 3 5 5 3 Adhesiveness 5 5 4 54 3 3 5 4 4 Ink jet jetting stability 5 5 4 5 3 3 4 3 5 5

TABLE 7 Example 11 12 13 14 15 16 17 18 19 20 Printing pattern 2 2 2 2 22 2 2 2 2 Solvent 3-Methoxybutyl acetate 82  82  82  82  — — 82  82  82 82  TEGMBE — — — — 82  — — — — — DEGDEE — — — — — 82  — — — — OligomerCN9001 (bifunctional, Mw 3,250) 5 5 5 5 5 5 5 — 8 2 SHIKO UV-7600B(hexafunctional, 5 5 5 5 5 5 — 5 2 8 Mw 1,400) SHIKO UV-7550B(trifunctional, — — — — — — 5 — — — Mw 2,400) SHIKO UV-3310B(bifunctional, — — — — — — — 5 — — Mw 5,000) Resin Vinnol H14/36 2 2 2 22 2 2 2 2 2 Polymer- UV12 1 1 1 1 1 1 1 1 1 1 ization inhibitorPhotopoly- Irg819 3 3 3 3 3 3 3 3 3 3 merization Irg2959 1 1 1 1 1 1 1 11 1 initiator Polyether- KP109 (50% sol.) (SiO content: — — — — 1 1 1 11 1 modified 29% by mass, Mw 12,000) siloxane KF-96H-10,000 CS (SiOcontent: 1 — — — — — — — — — compound 20% by mass or more, Mw 70,000)KF-96H-30,000 CS (SiO content: — 1 — — — — — — — — 20% by mass or more,Mw 90,000) KF-96H-100,000 CS (SiO content: — — 1 — — — — — — — 20% bymass or more, Mw 100,000) BYK-UV 3500 (SiO content: — — — 1 — — — — — —30% by mass or more, Mw 3,500) Total (parts by mass) 100  100  100  100 100  100  100  100  100  100  Content of polyether-modified siloxanecompound 6 6 6 6 3 3 3 3 3 3 with respect to total solid content (% bymass) Content ratio of polymerizable compound with 10  10  10  10  20 20  20  20  20  20  respect to parts by mass of polyether-modifiedsiloxane compound 1 (parts by mass) Base Abrasion resistance 4 4 3 5 5 55 5 4 5 material: Bendability 5 5 5 4 5 5 5 5 5 3 ARES YP606 Chemicalresistance 4 4 5 5 5 5 5 5 4 4 Adhesiveness 4 4 5 3 5 5 5 5 5 5 Ink jetjetting stability 4 3 3 5 5 5 5 3 5 5

TABLE 8 Example 21 22 23 24 25 26 27 28 29 Printing pattern 2 2 2 2 2 11 1 1 Solvent 3-Methoxybutyl acetate 82  84  78 57 44 71 66 67 69Oligomer CN9001 (bifunctional, Mw 3,250) 5 5 2 10 10 12 12 12 12 SHIKOUV-7600B (hexafunctional, Mw 1,400) 5 5 2 10 10 3 3 3 3 Monomer PEA — —10 15 28 — — — — Resin Vinnol H14/36 — — 2 2 2 2 2 2 2 Vinnol H11/59 2 —— — — — — — — Polymer- UV12 1 1 1 1 1 1 1 1 1 ization inhibitorPhotopoly- Irg819 3 3 3 3 3 3 3 3 3 merization Irg2959 1 1 1 1 1 1 1 1 1initiator Mill base Cyan — — — — — 6 — — — Magenta — — — — — — 11 — —Yellow — — — — — — — 10 — Black — — — — — — — — 8 Polyether- KP109 (50%sol.) (SiO content: 29% by mass, 1 1 1 1 1 1 1 1 1 modified Mw 12,000)siloxane compound Total (parts by mass) 100  100  100 100 100 100 100100 100 Content of polyether-modified siloxane compound with 3 3 2 1 1 22 2 2 respect to total solid content (% by mass) Content ratio ofpolymerizable compound with respect to 20  20  28 70 96 30 30 30 30parts by mass of polyether-modified siloxane compound 1 (parts by mass)Base Abrasion resistance 5 5 4 4 4 5 5 5 5 material: Bendability 5 5 5 55 5 5 5 5 ARES YP606 Chemical resistance 5 4 3 4 3 4 5 5 4 Adhesiveness5 4 3 3 3 5 5 5 5 Ink jet jetting stability 3 5 5 5 5 4 4 4 4

TABLE 9 Comparative Example 1 2 3 4 5 6 Printing pattern 2 2 2 2 2 2Solvent 3-Methoxybutyl acetate 81  80  80  81  81  35  Oligomer CN9001(bifunctional, 5 5 5 5 5 8 Mw 3,250) SHIKO UV-7600B 5 5 5 5 5 7(hexafunctional, Mw 1,400) Monomer PEA — — — — — 40  Resin Vinnol H14/362 2 2 2 2 2 Vinnol H11/59 2 2 2 2 2 2 Polymer- UV12 1 1 1 1 1 1 izationinhibitor Photopoly- Irg819 3 3 3 3 3 3 merization Irg2959 1 1 1 1 1 1on initiator Mill base Cyan — — — — — — Magenta — — — — — — Yellow — — —— — — Black — — — — — — Polyether- KP109 (50% sol.) (SiO content: — — —— — 1 modified 29% by mass, Mw 12,000) siloxane BYK 331 (SiO content:10% by — 1 — — — — compound mass, Mw 2,500) Efka SL 3210 (SiO content:9% — — 1 — — — by mass, Mw 1,500) Polyether- KP105 (30% sol.) — — —3.3   — — modified siloxane compound Fluorine-based MEGAFACE RS-72-K — —— — 2.5   — surfactant (40% sol.) Total (parts by mass) 100  100  100 100  100  100  Content of polyether-modified siloxane 0 5 5 0 0 2compound with respect to total solid content (% by mass) Content ratioof polymerizable compound — 10  10  — — 110  with respect to parts bymass of polyether- modified siloxane compound 1 (parts by mass) BaseAbrasion resistance 1 2 1 1 2 3 material: Bendability 5 5 5 5 2 2 ARESYP606 Chemical resistance 2 2 2 2 2 2 Adhesiveness 5 3 3 3 3 3 Ink jetjetting stability 5 5 5 5 3 3 Comparative Example 7 8 9 10 11 Printingpattern 2 1 1 1 1 Solvent 3-Methoxybutyl acetate — 72  67  68  70 Oligomer CN9001 (bifunctional, 8 12  12  12  12  Mw 3,250) SHIKOUV-7600B 7 3 3 3 3 (hexafunctional, Mw 1,400) Monomer PEA 60  — — — —Resin Vinnol H14/36 2 2 2 2 2 Vinnol H11/59 2 — — — — Polymer- UV12 1 11 1 1 ization inhibitor Photopoly- Irg819 3 3 3 3 3 merization Irg2959 11 1 1 1 on initiator Mill base Cyan — 6 — — — Magenta — — 11  — — Yellow— — — 10  — Black — — — — 8 Polyether- KP109 (50% sol.) (SiO content: 1— — — — modified 29% by mass, Mw 12,000) siloxane BYK 331 (SiO content:10% by — — — — — compound mass, Mw 2,500) Efka SL 3210 (SiO content: 9%— — — — — by mass, Mw 1,500) Polyether- KP105 (30% sol.) — — — — —modified siloxane compound Fluorine-based MEGAFACE RS-72-K — — — — —surfactant (40% sol.) Total (parts by mass) 85  100  100  100  100 Content of polyether-modified siloxane 1 0 0 0   0.04 compound withrespect to total solid content (% by mass) Content ratio ofpolymerizable compound 150  — — — — with respect to parts by mass ofpolyether- modified siloxane compound 1 (parts by mass) Base Abrasionresistance 2 2 2 2 2 material: Bendability 2 5 5 5 5 ARES YP606 Chemicalresistance 2 3 2 2 3 Adhesiveness 3 5 5 5 5 Ink jet jetting stability 34 4 4 4

The “SiO content” in Tables 6 to 9 represents the content of thesiloxane structure in the compound.

As clearly seen from the results in Tables 6 to 9, it is found that in acase of using the ink jet liquid composition according to the embodimentof the present disclosure, and even in a case of using a base materialhaving a concave-convex shape as a base material, the abrasionresistance, bendability, chemical resistance, and adhesiveness of theobtained cured film are excellent.

In addition, as clearly seen from the results in Tables 6 to 9, the inkjet liquid composition according to the embodiment of the presentdisclosure has excellent ink jet jetting stability.

In addition, as shown in Examples 1 to 7 in Table 6, in a case where thecontent of the polyether-modified siloxane compound is 2% by mass ormore and 15% by mass or less with respect to the total solid content ofthe composition, the abrasion resistance, chemical resistance, andadhesiveness of the obtained cured film are further excellent, and theink jet jettability is further excellent.

As shown in Examples 1 and 10 in Table 6, in a case where the content ofthe siloxane structure of the polyether-modified siloxane compound is20% by mass or more with respect to the total mass of thepolyether-modified siloxane compound, the abrasion resistance, chemicalresistance, and adhesiveness of the obtained cured film are furtherexcellent.

As shown in Example 1 in Table 6 and Example 14 in Table 7, in a casewhere the weight-average molecular weight of the polyether-modifiedsiloxane compound is 5,000 or more, the bendability and adhesiveness ofthe obtained cured film are further excellent.

3. Printing of Pattern 2 after Changing Base Material

The abrasion resistance, bendability, chemical resistance, andadhesiveness of the prepared samples were evaluated based on theevaluation standards except that the liquid composition of Example 1, 8,or 9, or Comparative Example 1 or 2 shown in Table 10 was used on eachbase material shown in Table 10 as a transparent liquid composition bythe ink jet printer.

The evaluation results are collectively shown in Table 10.

TABLE 10 Comparative Example Example 1 8 9 1 2 Base Abrasion 5 5 4 1 2material: resistance CUPPUCCINO Bendability 5 5 5 5 5 CP-830 Chemical 55 4 2 2 resistance Adhesiveness 5 4 4 5 3 Base Abrasion 5 5 5 2 3material: resistance MPI 1005 Bendability 5 5 5 5 5 Chemical 5 5 5 2 2resistance Adhesiveness 5 5 4 5 4

In addition, the details of the base materials used in Examples aresummarized shown in Table 11.

TABLE 11 Base material Supplier L2/L1 Gloss polyvinyl MPI 1005 Averyproducts 1.05 chloride sheet corporation Polyvinyl chloride CUPPUCCINOYAMAPLAS 1.21 (PVC) leather CP-830 CO., LTD. Polyvinyl chloride ARESYP606 YAMAPLAS 1.33 (PVC) leather CO., LTD.

As shown in Tables 6 and 10, it is found that in a case of using the inkjet liquid composition according to the embodiment of the presentdisclosure, for the various base materials having a concave-convex shapeon the surface thereof, the abrasion resistance, bendability, chemicalresistance, and adhesiveness of the obtained cured film are excellent.

Example 30

4. Pattern for Both Decorative Layer and Protective Layer Using LiquidComposition According to Embodiment of Present Disclosure

The used liquid composition was introduced into the ink jet printer andthe pattern 2 was printed. As the coloring liquid composition, theliquid composition of Example 28 in Table 8 was used. A yellow solidimage of a size of 20 cm×12 cm was printed and a base material having adecorative layer formed thereon was prepared. The liquid composition ofExample 1 shown in Table 6 was used as a transparent liquid compositionto form a protective layer on the decorative layer. The abrasionresistance, bendability, chemical resistance, and adhesiveness wereevaluated for the prepared sample according to the above evaluationstandards.

In the evaluation results, the abrasion resistance was 5, thebendability was 5, the chemical resistance was 5, and the adhesivenesswas 5.

The entirety of the disclosure of Japanese Patent Application No.2017-037215 filled on Feb. 28, 2017, is incorporated herein byreference.

All documents, patent applications and technical standards mentionedherein are incorporated in the present specification by reference to thesame extent as if each individual document, patent application ortechnical standard was specifically and individually indicated to beincorporated by reference.

What is claimed is:
 1. An ink jet liquid composition comprising: anorganic solvent; a polymerizable compound; a photopolymerizationinitiator; and a polyether-modified siloxane compound having aweight-average molecular weight of 3,000 or more, wherein a content ofthe organic solvent is 40% by mass or more and 90% by mass or less withrespect to a total mass of the composition.
 2. The ink jet liquidcomposition according to claim 1, wherein a content of a siloxanestructure of the polyether-modified siloxane compound is 20% by mass ormore with respect to a total mass of the polyether-modified siloxanecompound.
 3. The ink jet liquid composition according to claim 1,wherein the polyether-modified siloxane compound has a weight-averagemolecular weight of 5,000 or more and 100,000 or less.
 4. The ink jetliquid composition according to claim 1, wherein a content of thepolyether-modified siloxane compound is 2% by mass or more and 15% bymass or less with respect to a total solid content of the composition.5. The ink jet liquid composition according to claim 1, wherein a massratio of the polyether-modified siloxane compound and the polymerizablecompound is polyether-modified siloxane compound: polymerizablecompound=1:5 to 1:30.
 6. The ink jet liquid composition according toclaim 1, wherein the polymerizable compound includes a bifunctionalurethane acrylate oligomer.
 7. The ink jet liquid composition accordingto claim 6, wherein the bifunctional urethane acrylate oligomer has aweight-average molecular weight of 3,000 or more and 20,000 or less. 8.The ink jet liquid composition according to claim 1, wherein a colorantis not contained.
 9. The ink jet liquid composition according to claim 1that is an ink jet liquid composition to be applied to a base materialhaving a concave-convex shape in at least a part of a surface.
 10. Anink jet recording method comprising: a step of applying the ink jetliquid composition according to claim 1 to a base material by an ink jetrecording head.
 11. The ink jet recording method according to claim 10,wherein the base material is a base material having a concave-convexshape in at least a part of a surface.
 12. An ink jet recording methodcomprising: a step of preparing a base material having a decorativelayer formed thereon; a step of applying the ink jet liquid compositionaccording to claim 8 to the decorative layer by an ink jet recordinghead; a step of drying the ink jet liquid composition on the decorativelayer by applying heat; and a step of curing the ink jet liquidcomposition by irradiating the ink jet liquid composition with anultraviolet ray, wherein the base material having the decorative layerformed thereon has a concave-convex shape in at least a part of asurface.